Device for treating keratin fibers

ABSTRACT

Device for treating keratin fibers, which comprises a vibration generator and a vibration transmitter, in which the vibration transmitter is secured on the hair during the treatment, and in which vibrations are transmitted to the keratin fibers in this clamped position during the treatment.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims benefit under 35 U.S.C. §119(e) of U.S.Provisional Application No. 60,541,123, filed Feb. 2, 2004. Thisapplication also claims priority under 35 U.S.C. § 120 of GermanApplication DE 10 2004 005 092.9, filed Feb. 2, 2004.

BACKGROUND OF THE INVENTION

The present invention pertains to the field of keratin fiber treatment.In particular, the invention concerns a treatment device for treatingkeratin fibers, a method for treating keratin fibers, the use of atreatment device for dyeing or bleaching a person's hair, andpreparations for dyeing or bleaching keratin fibers.

The treatment of keratin fibers, especially hair, can have variousobjectives. For one thing, the treatment can have the purpose of shapingthe keratin fibers. For example, the keratin fibers can be shaped intowaves, or wavy keratin fibers can be straightened by suitable treatment.Human hair is now being treated in many different ways with haircosmetic products, such as hair dyes, blond-bleaching preparations,waving lotions, straightening agents, hair treatments, and otherhair-care preparations. In this regard, products for changing the colorof hair are becoming increasingly important. So-called oxidation dyesare used for long-lasting intensive dyeing with suitable fastnessproperties. Dyes of this type usually contain oxidation dyeintermediates, so-called developer components. Active substances ofthese kinds, in combination with a developer lotion, producelong-lasting color changes in the hair by oxidation. Ammonia in thedyeing cream loosens the hair structure and allows the dye products topenetrate the interior of the hair (cortex). The oxidation processcauses physically small compounds to become large-molecular compounds,which become firmly coupled in the hair structure.

For temporary dyeing, customary dyeing or tinting agents are used, whichcontain so-called direct dyes as the dyeing components. These dyescomprise dye molecules that are directly absorbed by the hair and do notrequire an oxidation process to develop the dye. The dyeing intensityand the stability of these products depend on the number of hairwashings. It is the nature of this product category that continuouscolor loss occurs.

The mechanism of action of blond-bleaching preparations is fundamentallydifferent from that of the aforementioned dyes. A decolorizing bleachingprocess is initiated by the application to the hair of products thatcontain persulfates to the hair. They decolorize the natural pigmentmolecules, such as melanin, as well as any synthetic dyes that mayalready be present in the hair. The persulfate-containing preparationsare activated by a developer lotion, which is added immediately beforeapplication. The desired degree of brightening can be varied by thelength of time the preparation is allowed to act.

To intensify the treatment or to accelerate it, it is well known, forexample, that heat can be used during the treatment. In this regard,there are heating hoods, which, for example, are lowered over the headof a person whose hair is being treated.

In addition, WO 03/049712 and WO 03/020070 describe a comb-likeultrasonic device for treating hair or other fibers. An ultrasonicdevice of this type comprises an ultrasonic generator and a combconnected with the ultrasonic generator. To use this device, theultrasonic generator is turned on, and the individual strands of hair tobe treated are combed with the comb. This means, for example, that if adyeing process is to be improved through the use of this ultrasonicdevice, a hairdresser or the person handling the ultrasonic devicerepeatedly combs through the strands of hair to be dyed with the comb.

The use of an ultrasonic device of this type presents certain problemsin a modern salon operation, since it takes the person handling theultrasonic device a very long time to repeatedly go over all of theperson's hair one tuft at a time. Especially in the case of long hair,the time required for this is considerable.

SUMMARY OF THE INVENTION

The objective of the present invention is to specify an improvedtreatment device.

This objective is achieved by a specific embodiment of the invention, asspecified in claim 1.

Additional embodiments and refinements of the present invention areobjects of the dependent claims.

In accordance with an advantageous embodiment of the present invention,a treatment device for treating keratin fibers is specified, which has avibration generator for generating vibrations and a vibrationtransmitter, which is connected with the vibration generator, fortransmitting vibrations to the keratin fibers. The vibration transmitterhas sections that can be brought into a treatment position, in which thekeratin fibers are secured between the sections. For example, thevibration transmitter can be realized in the form of a metal clip orclamp. The keratin fibers are preferably secured in such a way that thevibration transmitter does not slip from the keratin fibers during thetreatment, i.e., in such a way that it does not slip, e.g., due to itsown weight, from the clamped keratin fibers, such as tufts of hair.

This device has the advantage that it is merely necessary for the personoperating it, for example, for the purpose of treating a person's hair,to apply the vibration transmitter to the hair to be dyed. The treatmentcan then be performed without the person operating the device having tocarry out any other action. After the treatment, the vibrationtransmitter is removed from the hair and, for example, hung on asuitable holder. Preferably, several vibration transmitters areprovided.

In accordance with another advantageous embodiment of the presentinvention, a treatment device for treating hair is specified, whichcomprises a hood that is suitable for at least partially enclosingregions of the head of a person whose hair is to be treated. Inaddition, a vapor generator is provided for producing vapor. The vaporgenerator is connected with the hood in such a way that the vapor thatis generated is fed into the hood and conveyed to the hair through smallholes provided in the hood. Furthermore, a vibration generator isprovided, which causes the vapor to vibrate, so that the vibrations aretransmitted to the hair in the area of the hood.

In accordance with this embodiment, vibrations are transmitted to thehair in an advantageous way without contact via a medium, namely, thevapor. The micromovements of the hair caused by the vibrations allow abetter hair treatment. For example, improved hair dyeing can be achievedin this way, as well as better shaping or straightening of the hair.Especially the combination of the vapor heat and the micromovementproduced in the hair can be advantageous.

In accordance with another advantageous embodiment of the presentinvention, a treatment device is specified, which has means fortransmitting vibrations, which are formed as partially elastic fingers,which at least partially surround the area of the head in which the hairis located.

This makes a very easily handled hair treatment device available. Duringtreatment, for example, the device can be supported on a holder, whilethe vibration transmitter is being used on the hair.

The use of the treatment device of the invention for hair dyeing orbleaching is especially advantageous. The use of vibrations or waves inthe ultrasonic range or even in the audible range, for example, kHz,allows the active substance combinations of the hair treatmentpreparation to penetrate the hair faster. Furthermore, deeperpenetration of the active substances into the fiber sheath of the hairand thus improved stability of the products produced by the dyeingprocess can be achieved. In addition, a significant increase in colorintensity can be achieved. The power of a vibration generator of thetype that can be used in the treatment device of the present inventionis, for example, in the range of 5 to 200 watts. The power is preferablyon the order of 100 watts. Examples of vibration generators that can beused are resonators or multivibrators, such as those used, for example,in power whistles and sirens. In addition, it is possible to use, forexample, magnetostrictive transducers, piezoelectric transducers, andpiezomagnetic transducers, for example, nickel-copper-cobalt ferrites.

Preferred embodiments of the present invention are described below withreference to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a three-dimensional view of a first embodiment of atreatment device in accordance with the present invention.

FIG. 2 shows a three-dimensional view of the treatment device of FIG. 1during its use.

FIG. 3 shows a three-dimensional detail view of the treatment device ofFIG. 1.

FIG. 4 shows a top view of an embodiment of a vibration transmitter inaccordance with the present invention, of a type which can be used, forexample, in the first embodiment of the treatment device in FIG. 1.

FIG. 5 shows a top view of another embodiment of a vibration transmitterin accordance with the present invention, of a type which can be used,for example, in the first embodiment of the treatment device in FIG. 1.

FIG. 6 shows a sectional view of another embodiment of a vibrationtransmitter with a tuft of hair wrapped in foil, of a type which can beused, for example, in the first embodiment of the treatment device inFIG. 1.

FIG. 7 shows a top view of the vibration transmitter of FIG. 6.

FIG. 8 shows a side sectional view of a second embodiment of a treatmentdevice for treating keratin fibers in accordance with the presentinvention.

FIG. 9 shows a simplified view of a third embodiment of a treatmentdevice for treating hair in accordance with the present invention.

FIG. 10 shows a simplified view of a fourth embodiment of a treatmentdevice for treating hair in accordance with the present invention.

FIG. 11 shows a simplified view of a fifth embodiment of a treatmentdevice for treating hair in accordance with the present invention.

FIG. 12 shows a three-dimensional view of a clip for transmittingvibrations in the fifth embodiment of the treatment device of FIG. 11.

FIG. 13 shows a side sectional view of a second variant of the secondembodiment of a treatment device for treating keratin fibers inaccordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following description of the drawings, the same reference numbersare used for elements which are the same or which correspond to eachother.

FIG. 1 shows a three-dimensional view of a first embodiment of atreatment device in accordance with the present invention. As FIG. 1shows the treatment device has three operating arms 2, 4, and 6, whichare preferably movably mounted on a stand 8. The operating arms 2, 4,and 6 are preferably movably mounted on the stand 8 in a way that allowseach of them to be moved in three dimensions. Each operating arm 2, 4,and 6 is provided with recesses or projections, on which severalvibration transmitters 12 can be removably placed. The vibrationtransmitters 12 are used to transmit vibrations, for example, in theaudible frequency range or in the ultrasonic range, to keratin fibers,such as a person's hair. The vibration transmitters 12 are connected toa control unit 16 by cables or suitable vibration transmission lines.The stand 8 is preferably supported on a foundation 10 that is fittedwith rollers.

As FIG. 1 shows, the vibration transmitters 12 are equally distributedon the three operating arms 2, 4, and 6. In FIG. 1, eleven vibrationtransmitters 12 are provided per operating arm, so that a total of 33vibration transmitters 12 are provided. Naturally, a larger or smallernumber of vibration transmitters can be provided in accordance with thepresent invention. For example, nine to twelve vibration transmittersare sufficient for certain applications. For applications in which alarge amount of hair, e.g., very long hair, is to be dyed, a total ofsixty vibration transmitters, for example, may be advantageous.

The vibration transmitters can be designed, for example, as light-weighthair clips, which are applied by hand to the person's hair, where theythen remain during the entire treatment, for example, for the entirereaction time of the dye or bleach used in the dyeing or bleachingprocess.

A vibration generator is housed in the control unit 16. The vibrationgenerator may be, for example, a piezomagnetic or piezoelectricvibration generator that is capable of producing frequencies on theorder of, for example, 5 kHz. However, the vibration generator can alsobe designed to generate frequencies in the ultrasonic range. Thevibration generator is preferably designed to generate frequencies inthe power range of 5 to 200 watts. The vibration generator preferablygenerates a power of 100 watts.

In a variant of this embodiment, instead of one vibration generatorbeing provided in the control unit 16, a large number of small vibrationgenerators can be provided in or on the vibration transmitters 12. Inthis way, it is not necessary to transmit the vibration energy from thevibration generator in the control unit 16 to the vibration transmitters12, but rather the vibrations are produced directly on the vibrationtransmitters 12, which, for example, are designed as hair clips.

The control unit 16 has means for adjusting the display and thesettings, so that, for example, the frequency generated by the vibrationgenerator can be adjusted, a treatment time can be set, and/or the powersetting of the vibration transmitters can be adjusted.

To carry out a treatment, the vibration transmitters 12 are applied byhand to the person's hair, for example, by a hairdresser, where theythen remain, for example, during a hair dyeing treatment, for the entirereaction time of the dye or bleach used in the dyeing or bleachingprocess. Usually, the hair to be dyed is treated in tufts with thedyeing or bleaching agent. The tufts of hair are then wrapped, forexample, in aluminum foil, the corners of which are folded down toproduce a small pocket. This pocket prevents the dyeing or bleachingagent from running out during the application. Instead of aluminum foil,it is also possible to use wax foil or PE foil.

Naturally, the treatment device in accordance with the present inventioncan also be used without foil pockets of this type.

The vibration transmitters, i.e., the clips, are clipped onto theindividual foil pockets. About 60 foil pockets are usually needed forthis type of hair treatment. If each vibration transmitter or clip isclipped onto two foil pockets, it is thus advantageous for 30 vibrationtransmitters 12 to be available.

Since each vibration transmitter 12 is connected by vibrationtransmission lines 14 (when the vibration generator is installed in thecontrol unit 16) or power supply lines 14 (when the vibration generatorsare provided directly on the power transmitters 12), it is advantageousfor the freedom of movement of the person, i.e., for example, a hairsalon customer, not to be overly restricted and for the person to beallowed to assume a comfortable, usually seated, position.

The clip is preferably designed in such a way that it can be easilyapplied to and removed from the foil-wrapped tufts of hair by hand. Tothis end, the clip may, for example, be provided with a spring, whichensures a firm grip of the clip on the foil pocket or on the tuft ofhair, but prevents strong squeezing of the foil or the tuft of hair. Thebasic dimensions of the clip are, for example 3 cm by 8 cm, which thusessentially correspond to the basic dimensions of a customary foilpocket.

FIG. 2 shows the treatment device of FIG. 1 during its use. As thedrawing shows, the outer dimensions of the stand 8 and the operatingarms 2, 4, and 6 are preferably such that they are arranged to the leftof, the right of, and above the head of a seated person 22, so that thedistance between each operating arm 2, 4, and 6 and the head of theperson 22 is about 10-30 cm. This ensures that the person 22 hassufficient freedom of movement during the treatment. In FIG. 2, foilpockets 20 are shown in the hair of the person 22, and the vibrationtransmitters 12 can now be clipped onto the foil pockets.

FIG. 3 shows a three-dimensional detail view of the treatment device ofFIG. 1. As the drawing shows, the operating arms 4 and 6 are arrangedopposite each other and essentially horizontally. Mounting devices, suchas projections, on which the vibration transmitters 12 are clipped, canbe provided on the upper side of the operating arms 2, 4, and 6. It isalso possible to provide recesses in the operating arms 2, 4, and 6,into which the vibration transmitters 12 are inserted. This makes itpossible for them be held in a resting position on the operating arms 2,4, and 6, so that, for example, the treatment device can be rolled to adifferent place without the vibration transmitters 12 falling off.

Furthermore, as FIG. 3 shows, a hand grip 30 can be provided on thecontrol unit 16 to simplify the handling of the treatment device.

FIG. 4 shows a top view of a vibration transmitter 12, as it can beused, e.g., in the treatment device shown in FIG. 1. The vibrationtransmitter 12 shown in FIG. 4 comprises two flat elements 50, which inthe closed state are arranged a small distance apart and essentiallyparallel to each other, and these flat elements 50 are preferablydesigned as small aluminum plates. For example, these small aluminumplates have dimensions of 5 cm by 8 cm. The small aluminum plates 50 arejoined by a spring 52 at one of their two shorter ends. The spring 52exerts a force on the plates 50 in such a way that the plates 50 arelightly pressed together in the closed state. The spring tension ispreferably of sufficient magnitude that, when the spring-tensionedplates 50 are slipped onto the foil pockets, sufficient spring tensionis applied to prevent the vibration transmitter 12 from slipping off thefoil pocket under its own weight, but not so much pressure is applied tothe foil pocket that an active agent applied to the hair in the foilpocket is squeezed out. In addition, the vibration transmitter 12 has agrip section 54, which serves both to press the plates 50 together andto allow the vibration transmitter 12 to be handled. Basically, thisvibration transmitter 12 can be designed like a clothespin or a hairclip.

It is also possible for there to be only one small aluminum plate 50instead of two and for the other plate 50 to be made of plastic.

As noted earlier, it is also possible to provide a vibration generator,for example, in the grip section 54 of the vibration transmitter. Thisvibration generator generates vibrations, which are then applied to theair through the small plates 50. Furthermore, it is possible, forexample, to provide a vibration generator on one or both of the smallplates 50. The vibration transmitter can be connected to the treatmentdevice, especially to the control unit 16, by a vibration transmissionline or power supply line 14.

FIG. 5 shows a top view of another embodiment of a vibration transmitterin accordance with the present invention. The vibration transmitter 12shown in FIG. 5 is essentially the same as the vibration transmitter 12shown in FIG. 4, except that the plates 50 are provided with cut-outsections 56, so that the plates 50 have the shape of a fork in the topview. In this way, it is possible, for example, to reduce the weight ofthe vibration transmitters but nevertheless to transmit the vibrationsto the hair or the foil pocket. Instead of the cut-out section 56, thesmall plates 50 can be provided with holes.

FIG. 6 shows a sectional side view of another embodiment of a vibrationtransmitter 12 in accordance with the present invention. As the drawingshows, the vibration transmitter 12 has a spring 52, which presses theregions 74 against each other. In the view shown in FIG. 6, a foilpacket 70 with a tuft of hair 72 is held between the regions 74. As FIG.6 shows, the vibration transmitter 12 is preferably designed in such away that a major portion of the foil packet or foil pocket 70 isenclosed by the regions 74.

FIG. 7 shows a top view of the vibration transmitter 12 arranged on thefoil pocket 70. As the drawing shows, the regions 74 are designed as aU-shaped section of wire.

As noted above, in the present invention, vibrations are transmitted tothe hair to be treated. These vibrations are, for example, in theaudible range or in the ultrasonic range. These vibrations produce, forexample, micromovements of the hair. For example, a cavitation effectcan also be produced by these vibrations. The application of thevibrations to the hair also often leads to a temperature increase. Inany case, it can be stated that, for example, this type of applicationof vibrations to the hair significantly reduces the amount of time theactive hair-dyeing or hair-bleaching agents must act on the hair. Inaddition, more intensive and longer-lasting dyeing can be achieved,since the active agent can penetrate the fiber sheath more deeply. Theapplication of vibrations can also lead to a definite increase in colorintensity. These positive effects can advantageously reduce, e.g., theproportions of oxidation dye intermediates or ammonia in the hair-dyeingor hair-bleaching agents, which, for example, reduces the annoyance ofstrong odors for persons who come in contact with these agents. It isalso possible to achieve an advantageous reduction of the amounts ofactive substances and agents. Furthermore, subtler dyeing can beachieved.

FIG. 8 shows a side view of a second embodiment of a treatment device ofthe present invention. As the drawing shows, this treatment device has ahood 90, which is designed to surround regions of a person's head. Forexample, the hood 90 has essentially the dimensions of a conventionalcommercial drying hood. The hood 90 can be made, for example, of aplastic material. The hood 90 has an inner side 92 and an outer side 94.A large number of small holes 96 are provided on the inner side, i.e.,the side of the hood 90 that faces the hair to be treated. Instead ofholes, it is also possible to provide slits or openings of other, types.The hood 90 is connected to a vapor generator 98. The vapor generator 98is connected with the hood 90 in such a way that vapor produced in thevapor generator 98 is introduced into a space between the inner side 92and the outer side 94 of the hood 90 and is then conveyed through theholes 96 to the hair of the person to be treated. In addition, avibration generator 102 is provided, which transmits vibrations, forexample, via a vibration element 100, to the vapor or to a liquid, whichis evaporated. The vibration generator 102 can be provided withadjusting devices 104 for adjusting the power and/or frequency of thegenerated vibrations.

The vapor can be provided with vibrations, for example, in such a waythat the particles of liquid experience slight vibration, for example, amicrovibration, and in such a way that molecular vibration is producedin the liquid droplets that form the vapor. When water vapor is used, itis possible, for example, to produce a dipole vibration.

For example, the vibration element 100 can be refined in such a way thatthe vibration element 100 brings about atomization of a liquid toproduce an aerosol. For example, by dropping a liquid onto the vibrationelement 100, fine atomization can be produced in such a way that a veryfine aerosol is produced.

In accordance with a variation of this second embodiment (FIG. 13), oneor more sound generators (also known as vibration elements) can bemounted on the inner side (92) of the hood, independently of the holes(96); the sound generators arranged in this way transfer the vibrationsthrough the vapor phase to the hair to be treated. Although it issufficient, in accordance with the invention, to mount only a singlesound generator on the inner side of the hood, the mounting of severalsound generators on the inner side (92) of the hood can be preferred.Furthermore, it is preferred if these sound generators are uniformlydistributed over the inner side of the hood to allow uniformtransmission of the vibrations to the vapor around the head of theperson whose hair is to be treated.

These sound generators preferably consist of a radiating surface, one ormore resonators and an electromechanical transducer. In accordance withthe invention, the electromechanical transducer is preferably apiezoelectric transducer or a magnetostrictive transducer.

The radiating surface is preferably made of stainless steel or titaniumand preferably has a surface area of 100 to 10,000 mm², especially 1000to 8000 mm². A surface area of 7000 mm² can be especially preferred inaccordance with the invention. A rectangular geometry of the radiatingsurface is preferred in accordance with the invention, but any othergeometry is also possible, for example, square or circular. Theradiating surface can be mounted, for example, on a cylindricalattachment with a diameter of 10-100 mm, especially 35-65 mm and mostespecially 45-55 mm. This cylindrical attachment is constructed ofseveral disks with a piezoelectric transducer preferably located in thecenter and with a resonator on each side. With an arrangement of thistype, the radiating surface is preferably mounted on one of the tworesonators. As a result of this vibration of the piezoelectrictransducer, the whole cylindrical attachment in this refinement issubject to a change in length and transmits this vibration to theradiating surface. The piezoelectric transducer is excited by ahigh-frequency generator, preferably in the region of its resonancefrequency. Preferred frequencies to be used in accordance with theinvention are 20-50 kHz, especially 30-40 kHz and most preferably in thearea of 35 kHz.

In addition, it can also be preferred in accordance with the inventionnot to drive the piezoelectric transducer at a constant frequency, butrather to vary the frequency in a range of several hundred Hz (thefrequency is wobbled). IN this process, the high frequency is varied by0.1 to 1 kHz, preferably several times per second and especially 10times per second. At a basic frequency of, for example, 35 kHz, thisvariation causes the frequency to vary in a range of about 34 to 36 kHz.This modification produces a more uniform result on the fibers to betreated.

In accordance with the invention, it can also be preferred to usemechanical movement of the entire sound generator inside the vapor hoodto achieve a more uniform result. For example, the sound generator as awhole can be slowly moved back and forth or can also revolve in cyclicalpaths inside the hood. This can occur, for example, with a frequency onthe order of about 1 revolution per 10-300 seconds and preferably about1 revolution per 10 seconds. When several sound generators are used, itis also possible for all of them to be integrated in a motion of thistype. In accordance with the invention, it is also possible to combinefrequency wobbling with simultaneous mechanical movement of the entiresound generator. In this regard, the system is preferably optimized insuch a way that it allows maximum sound emission in a gaseous medium.

Methods and devices in which, for example, vibrations, such asultrasonic waves, can be transmitted to vapor are described in U.S. Pat.No. 3,211,159 and U.S. Pat. No. 4,085,893, which are herewithincorporated in the present disclosure by reference.

FIG. 9 shows a simplified view of a third embodiment of a treatmentdevice of the present invention. The treatment device shown in FIG. 9comprises vibration transmitters 120, which are formed as partiallyelastic fingers, which can be flipped from a resting position, in whichthey are shown in FIG. 9, into an operating position in such a way thatthe fingers 120 rest on an individual's hair. To this end, the vibrationtransmitters, which are movably mounted, for example, on a wall, by amounting device 122, are moved up to the head of, for example, a seatedperson, in such a way that a center 126, at which the vibrationtransmitters 120 come together and are attached to the mounting device122, rests on the person's hair basically near the whorl of hair at therear of the head. The fingers 120 flipped onto the hair can then be madeto conform to the shape of the person's head or hair, so that thefingers 120 are in contact with large areas of or a large portion of thehair to be treated. The fingers 120 can be made, for example, of plasticmaterials, such as PE, covered with metal foil. As FIG. 9 shows, avibration generator 124 is provided, which can be mounted in a suitableplace in the treatment device and transmits the vibrations to thefingers 120, through which the vibrations are in turn transmitted to thehair.

Instead of a central vibration generator 124, one or more vibrationgenerators can also be mounted on the fingers 120.

To distribute the vibrations as uniformly as possible to the hair, thehair can be pretreated with, for example, a vibration-conductingsubstance. For example, a good distribution of the vibrations aroundeach of the fingers 120 can be achieved by applying an aqueous liquid orgel to the hair.

FIG. 10 shows a fourth embodiment of a treatment device in accordancewith the present invention. The treatment device shown in FIG. 10 isessentially the same as the treatment device shown in FIG. 9, exceptthat a vibration transmission plate 130 that conforms to the curvatureof the head is provided instead of a large number of fingers. Thisslightly curved vibration transmission plate 130 is flexibly attached bythe mounting device 122, for example, to a stand or to a wall. Toperform the treatment, the vibration transmission plate 130 can beapplied to regions of the person's hair. This treatment device can beused, for example, in conjunction with a treatment device of the typeshown in FIG. 9 if a person has very long hair. The treatment deviceshown in FIG. 9 can be used in the immediate vicinity of the head forthe hair on the head down to about the neck region. For longer hair thatreaches, for example, to the lower back, the treatment device shown inFIG. 10 can be used by placing the vibration transmission plate 130 onthe hair in the region between the person's neck and lower back. In thisway, an efficient treatment can be ensured even for long hair.

FIG. 11 shows a simplified view of a fifth embodiment of a treatmentdevice in accordance with the present invention. As the drawing shows,this treatment device has a basically chair-like configuration with abase 140, which can be equipped with rollers, a seat 142, on which aperson can sit, and a back support 144, which is designed in such a waythat a person can lean back against it. A large number of vibrationtransmitters 146 is provided on the back support 144. A vibrationgenerator can be provided, for example, in the seat 142 and can beconnected by suitable vibration transmission lines with the vibrationtransmitters 146. It is also possible to provide individual vibrationgenerators in, on or near the vibration transmitters 146.

FIG. 12 shows a three-dimensional view of an embodiment of a vibrationtransmitter 146 that can be used, for example, in the treatment deviceillustrated in FIG. 11. The vibration transmitter 146 is connected withthe treatment device by a suitable line 148. The mechanical function ofthe vibration transmitter is essentially the same as that of aclothespin. When an operator presses the two handling regions 150together, the two clip regions 152 are opened or moved apart. Betweenthe handling regions 150 and the clip regions 152, there is a spring154, which, when the handling regions 150 are not being pressedtogether, forces the clip regions 152 to come together in a position inwhich they are essentially parallel to each other. A foil packet thatencloses hair and is arranged between the clip regions is thus heldbetween the clip regions 152. The spring tension of the spring 154 ispreferably strong enough that, when the vibration transmitter 146 isattached to a foil pocket, the weight of the vibration transmitter 146itself is supported on the foil packet or on the hair. On the otherhand, the spring tension of the spring 154 is weak enough to ensure thatthe foil packet is not pressed together to strongly, so that, forexample, an active substance that has been applied to the hair is notsqueezed out of the foil packet. The regions 152 and 150 can bealternately connected like a clothespin.

Vibrations can be transmitted to keratin fibers, for example, hair, bymeans of the embodiments described above. As described above, thetreatment devices are preferably designed in such a way that noattendance by the operator is necessary during the treatment. That is,the treatment device is set up, for example, vibration transmitters areapplied to the hair. The treatment is then begun. During the treatment,no attendance or supervision by, for example, a hairdresser or assistantis necessary. As soon as the treatment is finished, the vibrationtransmitters can then be removed. This simplifies the handling of thedevice and allows efficient treatment of a large number of persons inthe everyday routine of the hair salon.

As noted earlier, a treatment can involve the shaping of hair, thedyeing of hair, the bleaching of hair or the application of hairtreatment agents or hair-care preparations.

The vibrations transmitted to the keratin fibers can be in the audiblerange or even in the ultrasonic range. For example, an improvedtreatment can be achieved at a frequency of 5 kHz. However, it is alsopossible to obtain good results with frequencies in the range of 20 kHzto 200 kHz. Good results can also be achieved in higher frequencyranges. The power of the vibration generators that are used can varyfrom 5 to 200 watts. More powerful vibration transmitters are alsoconceivable. The total power of the vibration transmitters of atreatment device is advantageously on the order of 100 watts.

The treatment devices described above can be advantageously used forhair dyeing or bleaching. For example, agents for dyeing or bleachingkeratin fibers can be used which contain no chelant or chelating agent.A standard function of chelating agents or chelants is reduction ofvisible fiber damage caused by the simultaneous or subsequent use ofoxidative treatment steps involving bleaching or dyeing of the hair.Chelating agents accomplish this by fixing minerals that are bound inthe hair. To this end, it is necessary for the chelating agents to bebrought into contact with the hair as effectively as possible, so thatpreferably they quickly get into or penetrate the hair. Chelants orchelating agents (also known as chelants) pertain to a molecule that hastwo or more electron donor atoms, so that coordinate bonds can be formedwith a single ion. This results in the formation of a cyclic structureknown as a chelate. In particular, these are understood to mean diaminesor monoamine dipole acids or the like. Amine-based chelating agents arealso known, which supposedly improve the effectiveness of an oxidizingagent.

Described in a general way, chelating agents are always so-called, atleast bidentate molecules that form a ring or the like with the metalion to be formed.

Complexing agents of this type can also be used to bind or capture metalion impurities in water.

Accordingly, embodiments of agents for dyeing or bleaching keratinfibers in accordance with the present invention are specified ordescribed, which do not have to contain a chelant or chelating agent orin which chelants or chelating agents can be left out. These agents canbe advantageously used in conjunction with the treatment devices thatwere described earlier.

For the dyeing of keratin fibers, especially human hair, the so-calledoxidation dyes play a preferred role due to their intensive dyeing andgood fastness properties. Dyes of this type contain oxidation dyeintermediates, so-called developer components and coupler components.The developer components form the actual dyestuffs among themselvesunder the influence of oxidizing agents or atmospheric oxygen or bycoupling with one or more coupler components.

Primary aromatic amines with an additional free or substituted hydroxylor amino group in the para or ortho position, diaminopyridinederivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and2,4,5,6-tetraminopyrimidine and its derivatives are usually used asdeveloper components.

Specific members of these groups are p-phenylenediamine,p-toluylenediamine, 2,4,5,6-tetraminopyrimidine, p-aminophenol,N,N-bis(2-hydroxyethyl)-p-phenylenediamine,2-(2,5-diaminophenyl)ethanol, 2-(2,5-diaminophenoxy)ethanol,1-phenyl-3-carboxyamido-4-aminopyrazol-5-one, 4-amino-3-methylphenol,2-aminomethyl-4-aminophenol, 2-hydroxy-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triamino-4-hydroxypyrimidine,and1,3-N,N′-bis(2-hydroxyethyl)-N,N′-bis(4-aminophenyl)diaminopropan-2-ol.

-   -   m-Phenylenediamine derivatives, naphthols, resorcinol and        resorcinol derivatives, pyrazolones and m-aminophenols are        usually used as coupler components. The following substances are        especially suitable as coupler substances: 1-naphthol, 1,5-,        2,7-, and 1,7-dihydroxynaphthalene, 5-amino-2-methylphenol,        m-aminophenol, resorcinol, resorcinol monomethyl ether,        m-phenylenediamine, 1-phenyl-3-methylpyrazol-5-one,        2,4-dichloro-3-aminophenol, 1,3-bis(2,4-diaminophenoxy)propane,        2-chlororesorcinol, 4-chlororesorcinol,        2-chloro-6-methyl-3-aminophenol, 2-methyl resorcinol, 5-methyl        resorcinol, and 2-methyl-4-chloro-5-aminophenol.

Good oxidation dye intermediates should satisfy the followingrequirements above all: During the oxidative coupling, they must developthe desired color shades in sufficient intensity and fastness. Inaddition, they must have a good capacity for absorption on the fibers,and, especially in the case of human hair, there may be no appreciabledifferences between frayed hair and hair that has recently grown in(leveling capacity). They should be resistant to light, heat, sweat,friction and the action of chemical reducing agents, e.g., permanentwave liquids. Finally, if used as hair dyes, they should not stain thescalp very much, and, above all, they should be toxicologically anddermatologically safe. Furthermore, the dyeing produced byblond-bleaching should be readily removable from the hair if it turnsout that it does not conform to the desires of the individual person andis to be reversed.

In accordance with the invention, keratin fibers are understood to meanfurs, wool, feathers and especially human hair.

Primary aromatic amines with an additional free or substituted hydroxylor amino group in the para or ortho position, diaminopyridinederivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives, and2,4,5,6-tetraminopyrimidine and its derivatives are usually used asdeveloper components.

The use of a p-phenylenediamine derivative or one of its physiologicallytolerated salts can be preferred in accordance with the invention.p-Phenylenediamine derivatives of formula (E1) are especially preferred

in which

-   -   G¹ stands for a hydrogen atom, a C₁ to C₄ alkyl group, a C₁ to        C₄ monohydroxyalkyl group, a C₂ to C₄ polyhydroxyalkyl group, a        (C₁ to C₄)-alkoxy-(C₁ to C₄)-alkyl group, a 4′-aminophenyl        group, or a C₁ to C₄ alkyl group substituted with a        nitrogen-containing group, a phenyl group, or a 4′-aminophenyl        group;    -   G² stands for a hydrogen atom, a C₁ to C₄ alkyl group, a C₁ to        C₄ monohydroxyalkyl group, a C₂ to C₄ polyhydroxyalkyl group, a        (C₁ to C₄)-alkoxy-(C₁ to C₄)-alkyl group, or a C₁ to C₄ alkyl        group substituted with a nitrogen-containing group;    -   G³ stands for a hydrogen atom, a halogen atom, such as a        chlorine, bromine, iodine, or fluorine atom, a C₁ to C₄ alkyl        group, a C₁ to C₄ monohydroxyalkyl group, a C₂ to C₄        polyhydroxyalkyl group, a C₁ to C₄ hydroxyalkoxy group, a C₁ to        C₄ acetylaminoalkoxy group, a C₁ to C₄ mesylaminoalkoxy group,        or a C₁ to C₄ carbamoylaminoalkoxy group;    -   G⁴ stands for a hydrogen atom, a halogen atom, or a C₁ to C₄        alkyl group, or if G³ and G⁴ are in the ortho position relative        to each other, together they can form a bridging        α,β)-alkylenedioxo group, for example, an ethylenedioxy group.

Examples of the C₁ to C₄ alkyl groups specified as substituents in thecompounds in accordance with the invention are the groups methyl, ethyl,propyl, isopropyl, and butyl. Ethyl and methyl are preferred alkylgroups. Examples of preferred C₁ to C₄ alkoxy groups in accordance withthe invention are the methoxy group and the ethoxy group. Examples ofpreferred C₁ to C₄ hydroxyalkyl groups are the hydroxymethyl,2-hydroxyethyl, 3-hydroxypropyl, and 4-hydroxybutyl groups. A2-hydroxyethyl group is especially preferred. An especially preferred C₂to C₄ polyhydroxyalkyl group is the 1,2-dihydroxyethyl group. Examplesof halogen atoms that can be used in accordance with the invention areF, Cl, or Br atoms. Cl atoms are especially preferred. Other terms usedin accordance with the invention are derived from the definitions givenhere. Examples of nitrogen-containing groups in formula (E1) includeespecially amino groups, C₁ to C₄ monoalkylamino groups, C₁ to C₄dialkylamino groups, C₁ to C₄ trialkylammonium groups, C₁ to C₄monohydroxyalkylamino groups, imidazolinium, and ammonium.

Especially preferred p-phenylenediamines of formula (E1) are selectedfrom among p-phenylenediamine, p-toluylenediamine,2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine,2,6-dimethyl-p-phenylenediamine, 2,6-diethyl-p-phenylenediamine,2,5-dimethyl-p-phenylenediamine, N,N-dimethyl-p-phenylenediamine,N,N-diethyl-p-phenylenediamine, N,N-dipropyl-p-phenylenediamine,4-amino-3-methyl-(N,N-diethyl)aniline,N,N-bis(β-hydroxyethyl)-p-phenylenediamine,4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline,4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline,2-(β-hydroxyethyl)-p-phenylenediamine,2-(α,β-dihydroxyethyl)-p-phenylenediamine, 2-fluoro-p-phenylenediamine,2-isopropyl-p-phenylenediamine, N-(β-hydroxypropyl)-p-phenylenediamine,2-hydroxymethyl-p-phenylenediamine,N,N-dimethyl-3-methyl-p-phenylenediamine,N,N-(ethyl-β-hydroxyethyl)-p-phenylenediamine,N-(β,γ-dihydroxypropyl)-p-phenylenediamine,N-(4′-aminophenyl)-p-phenylenediamine, N-phenyl-p-phenylenediamine,2-(β-hydroxyethyloxy)-p-phenylenediamine,2-(β-acetylaminoethyloxy)-p-phenylenediamine,N-(β-methoxyethyl)-p-phenylenediamine, and 5,8-diaminobenzo-1,4-dioxane,and their physiologically tolerated salts.

-   -   p-Phenylenediamines of formula (E1) that are especially        preferred are p-phenylenediamine, p-toluylenediamine,        2-(β-hydroxyethyl)-p-phenylenediamine,        2-(α,β-dihydroxyethyl)-p-phenylenediamine, and        N,N-bis(β-hydroxyethyl)-p-phenylenediamine.

In accordance with the invention, compounds that contain at least twoaromatic nuclei that are substituted with amino and/or hydroxyl groupscan also be preferred for use as the developer component.

Binuclear developer components that can be used in the dye compositionsin accordance with the invention include especially compounds of formula(E2) below and their physiologically tolerated salts:

in which

-   -   Z¹ and Z², independently of each other, stand for a hydroxyl or        NH₂ group, which is possibly substituted by a C₁ to C₄ alkyl        group, by a C₁ to C₄ hydroxyalkyl group, and/or by a bridge Y,        or which is possibly part of a bridging ring system,    -   the bridge Y stands for an alkylene group with 1 to 14 carbon        atoms, for example, a linear or branched alkylene chain or an        alkylene ring, which alkylene group can be interrupted or        terminated by one or more nitrogen-containing groups and/or one        or more hetero atoms, such as oxygen, sulfur, or nitrogen atoms,        and can possibly be substituted by one or more hydroxyl or C₁ to        C₈ alkoxy groups, or a direct linkage,    -   G⁵ and G⁶, independently of each other, stand for a hydrogen or        halogen atom, a C₁ to C₄ alkyl group, a C₁ to C₄        monohydroxyalkyl group, a C₂ to C₄ polyhydroxyalkyl group, a C₁        to C₄ aminoalkyl group, or a direct linkage to the bridge Y,    -   G⁷, G⁸, G⁹, G¹⁰ G¹¹ and G¹², independently of one another, stand        for a hydrogen atom, a direct linkage to the bridge Y or a C₁ to        C₄ alkyl group, subject to the conditions that the compounds of        formula (E2) contain only one bridge Y per molecule, and the        compounds of formula (E2) contain at least one amino group,        which bears at least one hydrogen atom.

In accordance with the invention, the substituents used in formula (E2)are defined analogously to the details specified above.

Preferred binuclear developer components of formula (E2) are especiallythe following:N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropan-2-ol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-diethyl-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,bis(2-hydroxy-5-aminophenyl)methane,1,3-bis(2,5-diaminophenoxy)propan-2-ol,N,N′-bis(4′-aminophenyl)-1,4-diazacycloheptane,N,N′-bis(2-hydroxy-5-aminobenzyl)piperazine,N-(4′-aminophenyl)-p-phenylenediamine, and1,10-bis(2′,5′-diaminophenyl)-1,4,7,10-tetraoxadecane, and theirphysiologically tolerated salts.

Binuclear developer components of formula (E2) that are especiallypreferred areN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropan-2-ol,bis(2-hydroxy-5-aminophenyl)methane,0,1,3-bis(2,5-diaminophenoxy)propan-2-ol,N,N′-bis(4′-aminophenyl)-1,4-diazacycloheptane, and1,10-bis(2′,5′-diaminophenyl)-1,4′,7,10-tetraoxadecane, or one of theirphysiologically tolerated salts.

In accordance with the invention, bis(2-hydroxy-5-aminophenyl)methane isan especially preferred binuclear developer component of formula (E2).

In addition, in accordance with the invention, it can be preferred touse a p-aminophenol derivative or one of its physiologically toleratedsalts as the developer component. p-Amino-phenol derivatives of formula(E3) are especially preferred

in which

-   -   G¹³ stands for a hydrogen atom, a halogen atom, a C₁ to C₄ alkyl        group, a C₁ to C₄ monohydroxyalkyl group, a C₂ to C₄        polyhydroxyalkyl group, a (C₁ to C₄)-alkoxy-(C₁ to C₄)-alkyl        group, a C₁ to C₄ aminoalkyl group, a hydroxy-(C₁ to        C₄)-alkylamino group, a C₁ to C₄ hydroxyalkoxy group, a C₁ to C₄        hydroxyalkyl-(C₁ to C₄)-aminoalkyl group, or a (di-C₁ to        C₄-alkylamino)-(C₁ to C₄)-alkyl group,    -   G¹⁴ stands for a hydrogen or halogen atom, a C₁ to C₄ alkyl        group, a C₁ to C₄ monohydroxyalkyl group, a C₂ to C₄        polyhydroxyalkyl group, a (C₁ to C₄)-alkoxy-(C₁ to C₄)-alkyl        group, a C₁ to C₄ aminoalkyl group, or a C₁ to C₄ cyanoalkyl        group,    -   G¹⁵ stands for hydrogen, a C₁ to C₄ alkyl group, a C₁ to C₄        monohydroxyalkyl group, a C₂ to C₄ polyhydroxyalkyl group, a        phenyl group, or a benzyl group, and    -   G¹⁶ stands for hydrogen or a halogen atom.

In accordance with the invention, the substituents used in formula (E3)are defined analogously to the details specified above.

Preferred p-aminophenols of formula (E3) are especially p-aminophenol,N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol,2-hydroxymethylamino-4-aminophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-(hydroxyethoxy)phenol, 4-amino-2-methylphenol,4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol,4-amino-2-aminomethylphenol,4-amino-2-(β-hydroxyethylaminomethyl)phenol,4-amino-2-(α,β-dihydroxyethyl)phenol, 4-amino-2-fluorophenol,4-amino-2-chlorophenol, 4-amino-2,6-dichlorophenol,4-amino-2-(diethylaminomethyl)phenol, and their physiologicallytolerated salts.

Compounds of formula (E3) that are especially preferred arep-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(α,β-dihydroxyethyl)phenol, and4-amino-2-(diethylaminomethyl)phenol.

Furthermore, the developer component can be selected from amongo-aminophenol and its derivatives, for example, 2-amino-4-methylphenol,2-amino-5-methylphenol, or 2-amino-4-chlorophenol.

In addition, the developer component can be selected from amongheterocyclic developer components, for example, the pyridine,pyrimidine, pyrazole, pyrazole-pyrimidine derivatives, and theirphysiologically tolerated salts.

Preferred pyridine derivatives are especially the compounds described inthe patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine,2-(4′-methoxyphenyl)-amino-3-aminopyridine,2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)-amino-3-amino-6-methoxypyridine, and3,4-diaminopyridine.

Preferred pyrimidine derivatives are especially the compounds describedin German Patent DE 2 359 399, Japanese Early Disclosure JP 02019576 A2,or Early Disclosure WO 96/15765, such as 2,4,5,6-tetraminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2-dimethyl-4,5,6-triaminopyrimidine,2,4-dihydroxy-5,6-diaminopyrimidine, and 2,5,6-triaminopyrimidine.

Preferred pyrazole derivatives are especially the compounds described inthe patents DE 3 843 892 and DE 4 133 957 and patent applications WO94/08969, WO 94/08970, EP 740 931, and DE 195 43 988, such as4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)pyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(β-aminoethyl)-amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole, and3,5-diamino-4-(β-hydroxyethyl)-amino-1-methylpyrazole.

Preferred pyrazole-pyrimidine derivatives are especially the derivativesof pyrazole-[1,5-a]-pyrimidine of formula (E4) below and its tautomericforms if a tautomeric equilibrium exists

in which

-   -   G¹⁷, G¹⁸, G¹⁹ and G²⁰, independently of one another, stand for a        hydrogen atom, a C₁ to C₄ alkyl group, an aryl group, a C₁ to C₄        hydroxyalkyl group, a C₂ to C₄ polyhydroxyalkyl group, a (C₁ to        C₄)-alkoxy-(C₁ to C₄)-alkyl group, a C₁ to C₄ aminoalkyl group,        which may possibly be protected by an acetylureid group or a        sulfonyl group, a (C₁ to C₄)-alkylamino-(C₁ to C₄)-alkyl group,        a di-[(C₁ to C₄)-alkyl]-(C₁ to C₄)-aminoalkyl group, in which        the dialkyl groups possibly form a carbon ring or a heterocyclic        ring with 5 or 6 chain members, a C₁ to C₄ hydroxyalkyl, or a        di-(C₁ to C₄)-[hydroxyalkyl]-(C₁ to C₄)-aminoalkyl group,    -   the X groups, independently of one another, stand for a hydrogen        atom, a C₁ to C₄ alkyl group, an aryl group, a C₁ to C₄        hydroxyalkyl group, a C₂ to C₄ polyhydroxyalkyl group, a C₁ to        C₄ aminoalkyl group, (C₁ to C₄)-alkylamino-(C₁ to C₄)-alkyl        group, a di-[(C₁ to C₄)-alkyl]-(C₁ to C₄)— aminoalkyl group, in        which the dialkyl groups possibly form a carbon ring or a        heterocyclic ring with 5 or 6 chain members, C₁ to C₄        hydroxyalkyl or a di-(C₁ to C₄)-[hydroxyalkyl]-(C₁ to        C₄)-aminoalkyl group, an amino group, a C₁ to C₄ alkyl or di-(C₁        to C₄ hydroxyalkyl)-amino group, a halogen atom, a carboxylic        acid group, or a sulfonic acid group,    -   i has a value of 0, 1, 2, or 3,    -   p has a value of 0 or 1,    -   q has a value of 0 or 1, and    -   n has a value of 0 or 1,        subject to the conditions that    -   the sum of p+q is not equal to 0,    -   if p+q is equal to 2, n has a value of 0, and the groups NG¹⁷G¹⁸        and NG¹⁹G²⁰ occupy the positions (2,3); (5,6); (6,7); (3,5) or        (3,7).

In accordance with the invention, the substituents used in formula (E4)are defined analogously to the details specified above.

If the pyrazole-[1,5-a]-pyrimidine of formula (E4) above contains ahydroxyl group in one of the positions 2, 5, or 7 of the ring system, atautomeric equilibrium exists, which is described, for example, by thefollowing equilibrium equation:

Especially the following pyrazole-[1,5-a]-pyrimidines of formula (E4)above can be cited:

-   pyrazole-[1,5-a]-pyrimidine-3,7-diamine;-   2,5-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine;-   pyrazole-[1,5-a]-pyrimidine-3,5-diamine;-   2,7-dimethylpyrazole-[1,5-a]-pyrimidine-3,5-diamine;-   3-aminopyrazole-[1,5-a]-pyrimidine-7-ol;-   3-aminopyrazole-[1,5-a]-pyrimidine-5-ol;-   2-(3-aminopyrazole-[1,5-a]-pyrimidine-7-ylamino)ethanol;-   2-[(2-(7-aminopyrazole-[1,5-a]-pyrimidine-3-ylamino)ethanol;-   2-[(3-aminopyrazole-[1,5-a]-pyrimidine-7-yl)-(2-hydroxyethyl)-amino]ethanol;-   2-[(7-aminopyrazole-[1,5-a]-pyrimidine-3-yl)-(2-hydroxyethyl)-amino]ethanol;-   5,6-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine;-   2,6-dimethylpyrazole-[1,5-a]-pyrimidine-3,7-diamine;-   3-amino-7-dimethylamino-2,5-dimethylpyrazole-[1,5-a]-pyrimidine;    and their physiologically tolerated salts and their tautomeric forms    if a tautomeric equilibrium is present.

The pyrazole-[1,5-a]-pyrimidines of formula (E4) above can be prepared,as described in the literature, by cyclization, starting from anaminopyrazole or from hydrazine.

In another preferred embodiment, the dyes of the invention contain atleast one other coupler component.

-   -   m-Phenylenediamine derivatives, naphthols, resorcinol and        resorcinol derivatives, pyrazolones, and m-aminophenol        derivatives are usually used as coupler components. The        following substances are especially suitable as coupler        substances: 1-naphthol, 1,5-, 2,7-, and        1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, m-aminophenol,        resorcinol, resorcinol monomethyl ether, m-phenylenediamine,        1-phenyl-3-methylpyrazol-5-one, 2,4-dichloro-3-aminophenol,        1,3-bis(2′,4′-diaminophenoxy)propane, 2-chlororesorcinol,        4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol,        2-amino-3-hydroxypyridine, 2-methyl resorcinol, 5-methyl        resorcinol, and 2-methyl-4-chloro-5-aminophenol.

The following are preferred coupler components in accordance with theinvention:

-   -   m-aminophenol and its derivatives, for example,        5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol,        3-amino-2-chloro-6-methylphenol,        2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol,        3-trifluoroacetylamino-2-chloro-6-methylphenol,        5-amino-4-chloro-2-methylphenol,        5-amino-4-methoxy-2-methylphenol,        5-(2′-hydroxyethyl)-amino-2-methylphenol,        3-(diethylamino)phenol, 1,3-dihydroxy-5-(methylamino)benzene,        3-ethylamino-4-methylphenol, and 2,4-dichloro-3-aminophenol,    -   o-aminophenol and its derivatives,    -   m-diaminobenzene and its derivatives, for example,        2,4-diaminophenoxyethanol, 1,3-bis(2′,4′-diaminophenoxy)propane,        1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,        1,3-bis(2′,4′-diaminophenyl)propane,        2,6-bis(2′-hydroxyethylamino)-1-methylbenzene, and        1-amino-3-bis(2′-hydroxyethyl)-aminobenzene,    -   o-diaminobenzene and its derivatives, for example,        3,4-diaminobenzoic acid and 2,3-diamino-1-methylbenzene,    -   di- and trihydroxybenzene derivatives, for example, resorcinol,        resorcinol monomethyl ether, 2-methyl resorcinol, 5-methyl        resorcinol, 2,5-dimethyl resorcinol, 2-chlororesorcinol,        4-chlororesorcinol, pyrogallol, and 1,2,4-trihydroxybenzene,    -   pyridine derivatives, for example, 2,6-dihydroxypyridine,        2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine,        3-amino-2-methylamino-6-methoxypyridine,        2,6-dihydroxy-3,4-dimethylpyridine,        2,6-dihydroxy-4-methylpyridine, 2,6-diaminopyridine,        2,3-diamino-6-methoxypyridine, and        3,5-diamino-2,6-dimethoxypyridine,    -   naphthalene derivatives, for example, 1-naphthol,        2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol,        2-hydroxyethyl-1-naphthol, 1,5-dihydroxynaphthalene,        1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,        1,8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and        2,3-dihydroxynaphthalene,    -   morpholine derivatives, for example, 6-hydroxybenzomorpholine        and 6-aminobenzomorpholine,    -   quinoxaline derivatives, for example,        6-methyl-1,2,3,4-tetrahydroquinoxaline,    -   pyrazole derivatives, for example,        1-phenyl-3-methyl-pyrazol-5-one,    -   indole derivatives, for example, 4-hydroxyindole,        6-hydroxyindole, and 7-hydroxyindole,    -   pyrimidine derivatives, for example, 4,6-diaminopyrimidine,        4-amino-2,6-dihydroxypyrimidine,        2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine,        2-amino-4-methylpyrimidine,        2-amino-4-hydroxy-6-methylpyrimidine, and        4,6-dihydroxy-2-methylpyrimidine, or    -   methylenedioxybenzene derivatives, for example,        1-hydroxy-3,4-methylenedioxybenzene,        1-amino-3,4-methylenedioxybenzene, and        1-(2′-hydroxyethyl)-amino-3,4-methylenedioxybenzene.

Coupler components that are especially preferred in accordance with theinvention are 1-naphthol, 1,5-, 2,7-, and 1,7-dihydroxynaphthalene,3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine,resorcinol, 4-chlororesorcinol, 2-chloro-6-methyl-3-aminophenol,2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, and2,6-dihydroxy-3,4-dimethylpyridine.

The hair dyes of this embodiment of the invention contain both thedeveloper components and the coupler components, preferably in an amountof 0.005 to 20 wt. %, and especially in an amount of 0.1 to 5 wt. %, ineach case based on the total amount of oxidation dye. In this regard,developer components and coupler components are generally used inapproximately equimolar amounts. Although the use of equimolar amountshas been found to be advantageous, a certain excess of individualoxidation dye intermediates is not disadvantageous, so that developercomponents and coupler components can be present in a molar ratio of1:0.5 to 1:3, and especially 1:1 to 1:2.

In another embodiment of the present invention, the dyes can contain atleast one precursor of a natural analogue dyestuff. Indoles andindolines that have at least one hydroxyl or amino group, preferably asa substituent on the six-membered ring, are preferably used asprecursors of natural analogue dyestuffs. These groups can have furthersubstituents, e.g., in the form of an etherification or esterificationof the hydroxyl group or an alkylation of the amino group. In a secondpreferred embodiment, the dyes contain at least one indole and/orindoline derivative.

Derivatives of 5,6-dihydroxyindoline of formula (IIa) are especiallywell suited as precursors of natural analogue hair dyes

in which, independently of one another,

-   -   R¹ stands for hydrogen, a C₁-C₄ alkyl group, or a C₁-C₄        hydroxyalkyl group,    -   R² stands for hydrogen or a —COOH group, such that the —COOH        group can also be present in the form of a salt with a        physiologically tolerated cation,    -   R³ stands for hydrogen or a C₁-C₄ alkyl group,    -   R⁴ stands for hydrogen, a C₁-C₄ alkyl group, or a —CO—R⁶ group,        in which R⁶ stands for a C₁-C₄ alkyl group, and    -   R⁵ stands for one of the groups specified for R⁴,        and physiologically tolerated salts of these compounds with an        organic or inorganic acid.

Especially preferred derivatives of indoline are 5,6-dihydroxyindoline,N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline,N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline,5,6-dihydroxyindoline-2-carboxylic acid, as well as 6-hydroxyindoline,6-aminoindoline, and 4-aminoindoline.

Especially preferred compounds within this group areN-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline,N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline, andespecially 5,6-dihydroxyindoline.

In addition, derivatives of 5,6-dihydroxyindole of formula (IIb) areextremely well suited as precursors of natural analogue hair dyes.

in which, independently of one another,

-   -   R¹ stands for hydrogen, a C₁-C₄ alkyl group, or a C₁-C₄        hydroxyalkyl group,    -   R² stands for hydrogen or a —COOH group, such that the —COOH        group can also be present in the form of a salt with a        physiologically tolerated cation,    -   R³ stands for hydrogen or a C₁-C₄ alkyl group,    -   R⁴ stands for hydrogen, a C₁-C₄ alkyl group, or a —CO—R⁶ group,        in which R⁶ stands for a C₁-C₄ alkyl group, and    -   R⁵ stands for one of the groups specified for R⁴,        and physiologically tolerated salts of these compounds with an        organic or inorganic acid.

Especially preferred derivatives of indole are 5,6-dihydroxyindole,N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole,N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole,5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole,and 4-aminoindole.

Especially preferred compounds within this group areN-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole,N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, andespecially 5,6-dihydroxyindole.

The indoline and indole derivatives can be used in the dyes of theinvention both as free bases and in the form of their physiologicallytolerated salts with inorganic or organic acids, e.g., thehydrochlorides, sulfates, and hydrobromides. The indole or indolinederivatives are usually present in the dyes in amounts of 0.05 to 10 wt.%, and preferably 0.2 to 5 wt. %.

In accordance with another embodiment of the invention, it can bepreferred for the indoline or indole derivative to be present in thedyes in combination with at least one amino acid or one oligopeptide. Itis advantageous for the amino acid to be an α-amino acid; especiallypreferred α-amino acids are arginine, ornithine, lysine, serine, andhistidine, especially arginine.

In addition to the m-phenylenediamine derivatives of formula (E1) inaccordance with the invention, in another preferred embodiment of thepresent invention, the dyes of the invention can contain one or moredirect dyes to obtain the desired shading. Direct dyes are usuallynitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones, orindophenols. Preferred direct dyes are the following compounds known bytheir international designations or trade names: HC Yellow 2, HC Yellow4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow10, Acid Yellow 23, Acid Yellow 36, HC Orange 1, Disperse Orange 3, AcidOrange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red33, Acid Red 52, HC Red BN, Pigment Red 57:1, HC Blue 2, HC Blue 12,Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, DisperseViolet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, AcidBlack 1, and Acid Black 52, as well as 1,4-diamino-2-nitrobenzene,2-amino-4-nitrophenol, 1,4-bis(β-hydroxyethyl)-amino-2-nitrobenzene,3-nitro-4-(β-hydroxyethyl)-aminophenol,2-(2′-hydroxyethyl)amino-4,6-dinitrophenol,1-(2′-hydroxyethyl)amino-4-methyl-2-nitrobenzene,1-amino-4-(2′-hydroxyethyl)-amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,4-amino-2-nitrodiphenylamine-2′-carboxylic acid,6-nitro-1,2,3,4-tetrahydroxyquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid, and2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

In addition, the preparations of the invention can contain a cationicdirect dye. Especially preferred compounds of this type are

-   -   (a) cationic triphenylmethane dyes, for example, Basic Blue 7,        Basic Blue 26, Basic Violet 2, and Basic Violet 14,    -   (b) aromatic systems substituted with a quaternary nitrogen        group, for example, Basic Yellow 57, Basic Red 76, Basic Blue        99, Basic Brown 16, and Basic Brown 17, and    -   (c) direct dyes that contain a heterocyclic ring that has at        least one quaternary nitrogen atom, such as those specified in        EP 998 908 A2, claims 6 to 11, to which explicit reference is        herewith made.

Preferred cationic direct dyes of group (c) include especially thefollowing compounds:

The compounds of formulas (DZ1), (DZ3), and (DZ5), which are also knownby the names Basic Yellow 87, Basic Orange 31, and Basic Red 51, areespecially preferred cationic direct dyes of group (c).

The cationic direct dyes sold under the trade name Arianor® are alsoespecially preferred cationic direct dyes in accordance with theinvention.

The preparations in accordance with this embodiment of the inventionpreferably contain the direct dyes in an amount of 0.01 to 20 wt. %,based on the total dye.

In addition, the preparations of the invention can also containnaturally occurring dyes, such as those contained in henna red, hennaneutral, henna black, chamomile blossom, sandalwood, black tea, alderbuckthorn (Rhamnus frangula) bark, sage, logwood, madder root, catechu,sedre, and alkanet root.

It is not necessary for the oxidation dye intermediates or the directdyes to be homogeneous compounds, but rather the hair dyes in accordancewith the invention can contain minor amounts of other componentsoriginating from the production processes for the individual dyes,provided that these other components do not adversely affect the dyeingresult or have to be excluded for other reasons, e.g., toxicologicalreasons.

With respect to the dyestuffs that can be used in the hair dyeing andtinting agents in accordance with the invention, explicit reference isadditionally made to the monograph C. Zviak, The Science of Hair Care,Chapter 7 (pp. 248-250; direct dyes) and Chapter 8 (pp. 264-267;oxidation dye intermediates), published as Volume 7 of the seriesDermatology (Edited by C. Culnan and H. Maibach), Verlag Marcel Dekker,Inc., New York, Basel, 1986, and “European Inventory of Cosmetic RawMaterials”, published by the European Union and available on floppy diskfrom the Bundesverband Deutscher Industrie- und Handelsunternehmen fürArzneimittel, Reformwaren und Körperpflegemittel e.V. [German NationalIndustrial and Commercial Association for Drugs, Health Products, andToiletries], Mannheim.

The dyes of the invention can also contain all active substances,additives, and adjuvants known for preparations of this type. In manycases, the dyes contain at least one surfactant. It is basicallypossible to use not only anionic surfactants, but also zwitterionic,ampholytic, nonionic, and cationic surfactants. In many cases, however,it has been found to be advantageous to select the surfactants fromamong anionic, zwitterionic or nonionic surfactants.

All anionic surface-active substances suitable for use on the human bodyare suitable for use as anionic surfactants in preparations inaccordance with the invention. These substances are characterized by ananionic group that makes the substance soluble in water, e.g., acarboxylate, sulfate, sulfonate or phosphate group, and a lipophilicalkyl group with about 10-22 C atoms. In addition, the molecule cancontain glycol ether groups or polyglycol ether groups, ester, ether andamide groups, and hydroxyl groups. The following are examples ofsuitable anionic surfactants, each in the form of the sodium, potassium,ammonium and mono-, di-, and trialkanol ammonium salts with 2 or 3 Catoms in the alkanol group,

-   -   linear fatty acids with 10-22 C atoms (soaps),    -   ether carboxylic acids with the formula        R—O—(CH₂—CH₂O)_(x)—CH₂—COOH, in which R is a linear alkyl group        with 10-22 C atoms and x=0 or 1 to 16,    -   acyl sarcosides with 10-18 C atoms in the acyl group,    -   acyl taurides with 10-18 C atoms in the acyl group,    -   acyl isethionates with 10-18 C atoms in the acyl group,    -   sulfosuccinic monoalkyl and dialkyl esters with 8-18 C atoms in        the alkyl group and sulfosuccinic acid monoalkyl polyoxyethyl        esters with 8-18 C atoms in the alkyl group and 1-6 oxyethyl        groups,    -   linear alkane sulfonates with 12-18 C atoms,    -   linear α-olefin sulfonates with 12-18 C atoms,    -   α-sulfo fatty acid methyl esters of fatty acids with 12-18 C        atoms,    -   alkyl sulfates and alkyl polyglycol ether sulfates with the        formula R—O—(CH₂—CH₂O)_(x)—SO₃H, in which R is a preferably        linear alkyl group with 10-18 C atoms and x=0 or 1 to 12,    -   mixtures of surface-active hydroxysulfonates in accordance with        DE 37 25 030 A,    -   sulfated hydroxyalkyl polyethylene glycol ethers and/or        hydroxyalkylene propylene glycol ethers in accordance with DE 37        23 354 A,    -   sulfonates of unsaturated fatty acids with 12-24 C atoms and 1-6        double bonds in accordance with DE 39 26 344 A,    -   esters of tartaric acid and citric acid with alcohols that are        addition products of about 2-15 molecules of ethylene oxide        and/or propylene oxide to fatty alcohols with 8-22 C atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates, and ether carboxylic acids with 10-18 C atoms in the alkylgroup and up to 12 glycol ether groups in the molecule, and especiallysalts of saturated and especially unsaturated C₈-C₂₂ carboxylic acids,such as oleic acid, stearic acid, isostearic acid, and palmitic acid.

Nonionic surfactants contain as the hydrophilic group, e.g., a polyolgroup, a polyalkylene glycol ether group, or a combination of polyol andpolyglycol ether groups. The following are examples of compounds of thistype:

-   -   addition products of 2-30 moles of ethylene oxide and/or 0-5        moles of propylene oxide to linear fatty alcohols with 8-22 C        atoms, to fatty acids with 12-22 C atoms, and to alkyl phenols        with 8-15 C atoms in the alkyl group,    -   C₁₂-C₂₂ fatty acid monoesters and diesters of addition products        of 1-30 moles of ethylene oxide to glycerol,    -   C₈-C₂₂ alkyl monoglycosides and oligoglycosides and their        ethoxylated analogues, and    -   addition products of 5-60 moles of ethylene oxide to castor oil        and hydrogenated castor oil.

Preferred nonionic surfactants are alkyl polyglycosides with the generalformula R¹O-(Z)_(x). These compounds are characterized by the followingparameters.

The alkyl group R¹ contains 6-22 carbon atoms and can be both linear andbranched. Primary linear and 2-methyl-branched aliphatic groups arepreferred. Examples of alkyl groups of this type are 1-octyl, 1-decyl,1-lauryl, 1-myristyl, 1-cetyl, and 1-stearyl. 1-Octyl, 1-decyl,1-lauryl, and 1-myristyl are especially preferred. When so-called “oxoalcohols” are used as starting materials, compounds with an odd numberof carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides that can be used in accordance with theinvention may contain, for example, only one specific alkyl group R¹.However, these compounds are usually produced with natural fats and oilsor mineral oils as the starting materials. In this case, the alkylgroups R comprise mixtures corresponding to the starting compounds orcorresponding to the given processing of these compounds.

Alkyl polyglycosides that are especially preferred are those in which R¹comprises

-   -   essentially C₈ and C₁₀ alkyl groups,    -   essentially C₁₂ and C₁₄ alkyl groups,    -   essentially C₈ to C₁₆ alkyl groups, or    -   essentially C₁₂ to C₁₆ alkyl groups.

Any desired mono- or oligosaccharides can be used as the sugar buildingblock Z. Sugars with 5 or 6 carbon atoms and the correspondingoligosaccharides are usually used. Examples of sugars of this type areglucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose,altrose, mannose, gulose, idose, talose, and sucrose. Preferred sugarbuilding blocks are glucose, fructose, galactose, arabinose, andsucrose; glucose is especially preferred.

The alkyl polyglycosides that can be used in accordance with theinvention contain, on average, 1.1 to 5 sugar building blocks. Alkylpolyglycosides with values of x of 1.1 to 1.6 are preferred. Alkylglycosides in which x is 1.1 to 1.4 are especially preferred.

The alkyl glycosides can be used not only for their surfactant effectbut also to improve the fixation of fragrant components on the hair.Thus, when it is desired that an effect of a perfume oil on the hairextend beyond the duration of the hair treatment, the expert willpreferably fall back on this class of substances as a further ingredientof the preparations of the invention.

The alkoxylated homologues of the specified alkyl polyglycosides canalso be used in accordance with the invention. These homologues cancontain, on average, up to 10 ethylene oxide and/or propylene oxideunits per alkyl glycoside unit.

In addition, zwitterionic surfactants can be used, especially asco-surfactants. Zwitterionic surfactants are surface-active compoundsthat have at least one quaternary ammonium group and at least one—COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule. Especially well-suitedzwitterionic surfactants are the so-called betaines, such asN-alkyl-N,N-dimethylammonium glycinates, for example, cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammoniumglycinates, such as cocoacylaminopropyl dimethylammonium glycinate, and2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines with 8-18 C atomsin the alkyl or acyl group, as well ascocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theINCI name cocamidopropyl betaine.

Ampholytic surfactants are also suitable, especially as co-surfactants.Ampholytic surfactants are surface-active compounds which, in additionto a C₈-C₁₈ alkyl or acyl group, contain at least one free amino groupand at least one —COOH or —SO₃H group in the molecule and are capable offorming inner salts. Examples of suitable ampholytic surfactants areN-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionicacids, and alkylaminoacetic acids with 8-18 C atoms in the alkyl group.Especially preferred ampholytic surfactants areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate, andC₁₂₋₁₈-acylsarcosine.

Cationic surfactants that can be used in accordance with the inventioninclude especially those of the following types: quaternary ammoniumcompounds, esterquats, and amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, especiallychlorides and bromides, such as alkyl trimethylammonium chlorides,dialkyl dimethylammonium chlorides, and trialkyl methylammoniumchlorides, e.g., cetyltrimethylammonium chloride,stearyltrimethylammonium chloride, distearyldimethylammonium chloride,lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride,and tricetylmethylammonium chloride, as well as the imidazoliumcompounds known by the INCI names quaternium-27 and quaternium-83. Thelong alkyl chains of the aforementioned surfactants preferably have10-18 carbon atoms.

Esterquats are well-known substances that contain both at least oneester function and at least one quaternary ammonium group as astructural element. Preferred esterquats are quaternized ester salts offatty acids with triethanolamine, quaternized ester salts of fatty acidswith diethanol alkylamines, and quaternized ester salts of fatty acidswith 1,2-dihydroxypropyldialkylamines. Products of this type are sold,for example, under the trade names Stepantex®, Dehyquart®, andArmocare®. The products Armocare® VGH-70, anN,N-bis(2-palmitoyloxyethyl)dimethylammonium chloride, and Dehyquart®F-75, and Dehyquart® AU-35 are examples of these esterquats.

The alkyl amidoamines are usually produced by amidation of natural orsynthetic fatty acids and fatty acid cuts with dialkyl aminoamines. Acompound in this group of substances that is especially suitable inaccordance with the invention is stearylamidopropyl dimethylamine, whichis commercially available under the trade name Tegoamid® S 18.

Other cationic surfactants that can be used in accordance with theinvention are quaternized protein hydrolysates.

Cationic silicone oils are also suitable in accordance with theinvention, for example, the commercially available products Q2-7224(manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone),Dow Corning 929 Emulsion (containing a hydroxylamino-modified silicone,which is also known as amodimethicone), SM-2059 (manufacturer: GeneralElectric), SLM-55067 (manufacturer: Wacker), and Abil®-Quat 3270 and3272 (manufacturer: T. Goldschmidt; diquaternary polydimethylsiloxanes,quaternium-80).

An example of a quaternary sugar derivative that can be used as acationic surfactant is the commercial product Glucquat® 100, which inINCI nomenclature is a “lauryl methyl gluceth-10 hydroxypropyldimoniumchloride”.

The compounds with alkyl groups that are used as the surfactant can behomogeneous substances. However, it is generally preferred to producethese substances from natural raw materials of animal or vegetableorigin, so that mixtures of substances are obtained that have differentalkyl chain lengths, depending on the particular raw material.

The surfactants that are addition products of ethylene and/or propyleneoxide with fatty alcohols or derivatives of these addition products mayeither be products with a “normal” homologue distribution or productswith a restricted homologue distribution. “Normal” homologuedistributions are understood to mean mixtures of homologues obtained inthe reaction of fatty alcohols and alkylene oxides with the use ofalkali metals, alkali-metal hydroxides, or alkali-metal alcoholates ascatalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkaline-earth-metal salts ofether carboxylic acids, alkaline-earth-metal oxides, hydroxides, oralcoholates are used as catalysts. The use of products with restrictedhomologue distributions can be preferred.

In many cases the hair treatment preparations additionally contain atleast one conditioning polymer.

Cationic polymers are a first group of conditioning polymers. Within thecontext of the invention, cationic polymers are understood to bepolymers whose main chain and/or side chain contains a group that can be“temporarily” cationic or “permanently” cationic. “Permanently cationic”polymers in accordance with the invention are polymers that have acationic group, independently of the pH of the preparation. These aregenerally polymers that contain a quaternary nitrogen atom, for example,in the form of an ammonium group. Preferred cationic groups arequaternary ammonium groups. In particular, polymers in which thequaternary ammonium group is linked to a polymer main chain consistingof acrylic acid, methacrylic acid or their derivatives via a C₁₋₄hydrocarbon group have proven especially suitable.

Especially preferred cationic polymers are homopolymers of generalformula (G1-I)

in which R=—H or —CH₃; R², R³, and R⁴ are selected, independently of oneanother, from C₁₋₄ alkyl, alkenyl, or hydroxyalkyl groups; m=1, 2, 3, or4; n is a natural number; and X⁻ is a physiologically tolerated organicor inorganic anion; and copolymers that consist essentially of themonomer units specified in formula (G1-I) and nonionic monomer units.Among these polymers, polymers which are preferred in accordance withthe invention are those for which one of the following conditionsapplies:

-   -   R¹ stands for a methyl group    -   R², R³, and R⁴ stand for methyl groups    -   m has a value of 2.

Suitable physiologically tolerated anions X⁻ include, for example,halide ions, sulfate ions, phosphate ions, methosulfate ions, andorganic ions, such as lactate, citrate, tartrate, and acetate ions.Halide ions are preferred, especially chloride.

An especially suitable homopolymer ispoly(methacryloyloxyethyltrimethylammonium chloride), which may becrosslinked, if so desired. The INCI name of the compound ispolyquaternium-37. If desired, the crosslinking can be carried out withmultiply olefinically unsaturated compounds, for example,divinylbenzene, tetrallyloxyethane, methylenebisacrylamide, diallylether, polyallyl polyglyceryl ether, or allyl ethers of sugars or sugarderivatives, such as erythritol, pentaerythritol, arabitol, mannitol,sorbitol, sucrose, or glucose. Methylenebisacrylamide is a preferredcrosslinking agent.

The homopolymer is preferably used in the form of a nonaqueous polymerdispersion, which should have a polymer content of not less than 30 wt.%. Polymer dispersions of this type are commercially available under thenames Salcare® SC 95 (ca. 50% polymer component; other components:mineral oil (INCI name: mineral oil) and tridecylpolyoxypropylene/polyoxyethylene ether (INCI name: PPG-1 trideceth-6))and Salcare® SC 96 (ca. 50% polymer component; other components: mixtureof diesters of propylene glycol with a mixture of caprylic acid andcapric acid (INCI name: propylene glycol dicaprylate/dicaprate) andtridecyl polyoxypropylene/polyoxyethylene ether (INCI name: PPG-1trideceth-6)).

Copolymers with monomer units of formula (G1-I) preferably containacrylamide, methacrylamide, acrylic acid C₁₋₄ alkyl esters, andmethacrylic acid C₁₋₄ alkyl esters as nonionic monomer units. Of thesenonionic monomers, acrylamide is especially preferred. As in the case ofthe homopolymers described above, these copolymers can also becrosslinked. A copolymer that is preferred in accordance with theinvention is crosslinkedacrylamide/methacryloyloxyethyltrimethylammonium chloride copolymer.Copolymers of this type, in which the monomers are present in a ratio byweight of about 20:80, are commercially available as a ca. 50%nonaqueous polymer dispersion under the name Salcare® SC 92.

Examples of other preferred cationic polymers are:

-   -   quaternized cellulose derivatives, such as those which are        commercially available under the names Celquat® and Polymer JR®.        The compounds Celquat® H 100, Celquat® L 200 and Polymer JR® 400        are preferred quaternized cellulose derivatives,    -   cationic alkyl polyglycosides as described in German Patent DE        44 13 686,    -   cationized honey, for example, the commercial product Honeyquat®        50,    -   cationic guar derivatives, especially products sold under the        trade names Cosmedia® Guar and Jaguar    -   polysiloxanes with quaternary groups, such as the commercially        available products Q2-7224 (manufacturer: Dow Corning; a        stabilized trimethylsilylamodimethicone), Dow Corning® 929        Emulsion (containing a hydroxylamino-modified silicone, which is        also known as amodimethicone), SM-2059 (manufacturer: General        Electric), SLM-55067 (manufacturer: Wacker), and Abil®-Quat 3270        and 3272 (manufacturer: T. Goldschmidt; diquaternary        polydimethylsiloxanes, quaternium-80),    -   polymeric dimethyldiallylammonium salts and their copolymers        with esters and amides of acrylic acid and methacrylic acid;        examples of cationic polymers of this type are the commercially        available products Merquat® 100 (poly(dimethyldiallylammonium        chloride)) and Merquat® 550 (dimethyldiallylammonium        chloride/acrylamide copolymer),    -   copolymers of vinylpyrrolidone with quaternized derivatives of        dialkylaminoalkylacrylate and methacrylate, for example,        vinylpyrrolidone/-dimethylaminoethylmethacrylate copolymer        quaternized with diethyl sulfate; compounds of this type are        commercially available under the names Gafquat® 734 and Gafquat®        755,    -   vinylpyrrolidone/vinylimidazoliummethochloride copolymers, such        as those sold under the names Luviquat® FC 370, FC 550, FC 905,        and HM 552,    -   quaternized polyvinyl alcohol, and    -   the polymers known by the names polyquaternium 2, polyquaternium        17, polyquaternium 18, and polyquaternium 27, which have        quaternary nitrogen atoms in the main chain of the polymer.

Other cationic polymers that can be used are polymers known by the namepolyquaternium-24 (commercial product, e.g., Quatrisoft® LM 200). Thecopolymers of vinylpyrrolidone can also be used in accordance with theinvention, e.g., those which are commercially available under the tradenames Copolymer 845 (manufacturer: ISP), Gaffix® VC 713 (manufacturer:ISP), Gafquat® ASCP 1011, Gafquat® HS 110, Luviquat® 8155, and Luviquat®MS 370.

Other cationic polymers in accordance with the invention are theso-called “temporarily cationic” polymers. These polymers usuallycontain an amino group, which at certain pH's is present as a quaternaryammonium group and is thus cationic. Preferred polymers of this typeinclude, for example, chitosan and its derivatives, such as thecommercially available products Hydagen® CMF, Hydagen® HCMF, Kytamer®PC, and Chitolam® NB/101.

Preferred cationic polymers in accordance with the invention arecationic cellulose derivatives and chitosan and its derivatives,especially the commercial products Polymer® JR 400, Hydagen® HCMF, andKytamer® PC, cationic guar derivatives, cationic honey derivatives,especially the commercial product Honeyquat® 50, cationic alkylpolyglycosides as described in German Patent DE 44 13 686, and polymersof the type polyquaternium-37.

In addition, the cationic polymers include cationized proteinhydrolysates. The underlying protein hydrolysate can be derived fromanimals, for example, from collagen, milk or keratin, from plants, forexample, from wheat, corn, rice, potatoes, soybeans, or almonds, or frommarine life forms, for example, from fish collagen or algae, or it canbe obtained by bioengineering methods. The protein hydrolysates on whichthe cationic derivatives of the invention are based can be obtained fromthe corresponding proteins by a chemical hydrolysis, especially analkaline or acid hydrolysis, by an enzymatic hydrolysis and/or by acombination of the two types of hydrolysis. The hydrolysis of proteinsgenerally yields a protein hydrolysate with a molecular-weightdistribution from about 100 daltons to several thousand daltons.Preferred cationic protein hydrolysates are those whose underlyingprotein component has a molecular weight of 100 to 25,000 daltons, andpreferably 250 to 5,000 daltons. Cationic protein hydrolysates are alsounderstood to mean quaternized amino acids and their mixtures. Theprotein hydrolysates or the amino acids are often quaternized by meansof quaternary ammonium salts, for example,N,N-dimethyl-N-(n-alkyl)-N-(2-hydroxy-3-chloro-n-propyl) ammoniumhalides. Moreover, the cationic protein hydrolysates can also be furtherderivatized. Typical examples of cationic protein hydrolysates andderivatives in accordance with the invention are the commerciallyavailable products listed by the INCI names in “International CosmeticIngredient Dictionary and Handbook”, (Seventh Edition 1997, TheCosmetic, Toiletry, and Fragrance Association, 1101 17th. Street, N.W.,Suite 300, Washington, D.C. 20036-4702): cocodimonium hydroxypropylhydrolyzed collagen, cocodimonium hydroxypropyl, hydrolyzed casein,cocodimonium hydroxypropyl hydrolyzed collagen, cocodimoniumhydroxypropyl hydrolyzed hair keratin, cocodimonium hydroxypropylhydrolyzed keratin, cocodimonium hydroxypropyl hydrolyzed rice protein,cocodimonium hydroxypropyl hydrolyzed soy protein, cocodimoniumhydroxypropyl hydrolyzed wheat protein, hydroxypropyl argininelauryl/myristyl ether HCl, hydroxypropyltrimonium gelatin,hydroxypropyltrimonium hydrolyzed casein, hydroxypropyltrimoniumhydrolyzed collagen, hydroxypropyltrimonium hydrolyzed conchiolinprotein, hydroxypropyltrimonium hydrolyzed keratin,hydroxypropyltrimonium hydrolyzed rice bran protein,hydroxypropyltrimonium hydrolyzed soy protein, hydroxypropyl hydrolyzedvegetable protein, hydroxypropyltrimonium hydrolyzed wheat protein,hydroxypropyltrimonium hydrolyzed wheat protein/siloxysilicate,laurdimonium hydroxypropyl hydrolyzed soy protein, laurdimoniumhydroxypropyl hydrolyzed wheat protein, laurdimonium hydroxypropylhydrolyzed wheat protein/siloxysilicate, lauryldimonium hydroxypropylhydrolyzed casein, lauryldimonium hydroxypropyl hydrolyzed collagen,lauryldimonium hydroxypropyl hydrolyzed keratin, lauryldimoniumhydroxypropyl hydrolyzed soy protein, steardimonium hydroxypropylhydrolyzed casein, steardimonium hydroxypropyl hydrolyzed collagen,steardimonium hydroxypropyl hydrolyzed keratin, steardimoniumhydroxypropyl hydrolyzed rice protein, steardimonium hydroxypropylhydrolyzed soy protein, steardimonium hydroxypropyl hydrolyzed vegetableprotein, steardimonium hydroxypropyl hydrolyzed wheat protein,steardimonium hydroxyethyl hydrolyzed collagen, quaternium-76 hydrolyzedcollagen, quaternium-79 hydrolyzed collagen, quaternium-79 hydrolyzedkeratin, quaternium-79 hydrolyzed milk protein, quaternium-79 hydrolyzedsoy protein, and quaternium-79 hydrolyzed wheat protein.

The plant-based cationic protein hydrolysates and derivatives areespecially preferred.

Other conditioning polymers that can be used in accordance with theinvention are the amphoteric compounds specified in British EarlyDisclosure 2 104 091, European Early Disclosure 47 714, European EarlyDisclosure 217 274, European Early Disclosure 283 817, and German EarlyDisclosure 28 17 369.

Preferred amphoteric polymers are polymers that are composed essentiallyof

-   -   (a) monomers with quaternary ammonium groups of general formula        (II),        R¹—CH═CR²—CO-Z—(C_(n)H_(2n))—N⁽⁺⁾R³R⁴R⁵A⁽⁻⁾  (II)    -    in which R¹ and R², independently of each other, stand for        hydrogen or a methyl group, R³, R⁴ and R⁵, independently of one        another, stand for alkyl groups with 1 to 4 carbon atoms, Z        stands for an NH group or an oxygen atom, n is a whole number        from 2 to 5, and A⁽⁻⁾ is the anion of an organic or inorganic        acid, and    -   (b) monomeric carboxylic acids of general formula (III),        R⁶—CH═CR⁷—COOH  (III)    -    in which R⁶ and R⁷, independently of each other, are hydrogen        or a methyl group.

In accordance with the invention, these compounds can be used bothdirectly and in the form of their salts, which are obtained byneutralization of the polymers, for example, with an alkali hydroxide.In regard to the details of the preparation of these polymers, explicitreference is made to the contents of German Early Disclosure 39 29 973.Especially preferred polymers of this type are those in which themonomers of type (a) are characterized by the fact that R³, R⁴, and R⁵are methyl groups, Z is an NH group, and A⁽⁻⁾ is a halide,methoxysulfate, or ethoxysulfate ion; acrylamidopropyl trimethylammoniumchloride is an especially preferred monomer (a). The use of acrylic acidas monomer (b) in the aforesaid polymers is preferred.

The hair-care preparations preferably contain the conditioning polymersin an amount of 0.01 to 5 wt. %, and especially in an amount of 0.1 to 2wt. %, based on the total applied preparation.

Other suitable hair-conditioning compounds are phospholipids, forexample, soy lecithin, egg lecithin, and cephalins, and the substancesknown by the following INCI names: linoleamidopropyl PG-dimoniumchloride phosphate, cocamidopropyl PG-dimonium chloride phosphate, andstearamidopropyl PG-dimonium chloride phosphate. These compounds aresold, for example, by the company Mona, under the trade namesPhospholipid EFA®, Phospholipid PTC®, and Phospholipid SV®.

The preparations of the invention preferably contain the lipids inamounts of 0.01 to 10 wt. %, and especially 0.1 to 5 wt. %, based on thetotal applied preparation.

In addition, the dyes of the invention can contain other activesubstances, adjuvants, and additives, for example

-   -   nonionic polymers, such as vinylpyrrolidone/vinyl acrylate        copolymers, polyvinylpyrrolidone and vinylpyrrolidone/vinyl        acetate copolymers, and polysiloxanes,    -   cationic polymers, such as quaternized cellulose ethers,        polysiloxanes with quaternary groups, dimethyldiallylammonium        chloride polymers, acrylamide/dimethyldiallylammonium chloride        copolymers, dimethylaminoethylmethacrylate/vinylpyrrolidone        copolymers quaternized with diethyl sulfate,        vinylpyrrolidone/imidazoliniummethochloride copolymers, and        quaternized polyvinyl alcohol,    -   zwitterionic and amphoteric polymers, such as        acrylamidopropyltrimethylammonium chloride/acrylate copolymers        and octyl acrylamide/methyl methacrylate/tert-butylaminoethyl        methacrylate/2-hydroxypropyl methacrylate copolymers,    -   anionic polymers, such as polyacrylic acids, crosslinked        polyacrylic acids, vinyl acetate/crotonic acid copolymers,        vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl        maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic        anhydride copolymers, and acrylic acid/ethyl        acrylate/N-tert-butyl acrylamide terpolymers,    -   thickening agents, such as agar-agar, guar gum, alginates,        xanthan gum, gum arabic, karaya gum, locust bean flour, linseed        gums, dextrans, cellulose derivatives, e.g. methyl cellulose,        hydroxyalkyl cellulose, and carboxymethyl cellulose, starch        fractions and derivatives, such as amylose, amylopectin, and        dextrins, clays, e.g. bentonite, or fully synthetic        hydrocolloids, such as polyvinyl alcohol,    -   structuring agents, such as maleic acid and lactic acid,    -   hair-conditioning compounds, such as phospholipids, for example,        soy lecithin, egg lecithin, and cephalins,    -   protein hydrolysates, especially elastin, collagen, keratin,        milk protein, soy protein, and wheat protein hydrolysates, their        condensation products with fatty acids, and quaternized protein        hydrolysates,    -   perfume oils, dimethyl isosorbitol, and cyclodextrins,    -   solvents and solubilizers, such as ethanol, isopropanol,        ethylene glycol, propylene glycol, glycerol, and diethylene        glycol,    -   active substances that improve fiber structure, especially        mono-, di-, and oligosaccharides, such as glucose, galactose,        fructose, levulose, and lactose,    -   quaternized amines, such as        methyl-1-alkylamidoethyl-2-alkylimidazolinium methosulfate,    -   antifoaming agents, such as silicones,    -   dyes for coloring the preparation itself,    -   anti-dandruff active ingredients, such as piroctone olamine,        zinc omadine, and climbazole,    -   light stabilizers, especially derivatized benzophenones,        cinnamic acid derivatives, and triazines,    -   substances for adjusting pH, such as customary acids, especially        acidulants, and bases,    -   active substances such as allantoin, pyrrolidone carboxylic        acids and their salts, and bisabolol,    -   vitamins, provitamins, and vitamin precursors, especially those        that are members of the groups A, B₃, B₅, B₆, C, E, F, and H,    -   plant extracts, such as extracts of green tea, oak bark,        stinging nettle, witch hazel, hops, chamomile, lappa, horsetail,        hawthorn, linden flower, almond, aloe vera, spruce needle, horse        chestnut, sandalwood, juniper, coconut, mango, apricot, lemon,        wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch,        mallow, cuckooflower, wild thyme, yarrow, thyme, balm,        restharrow, coltsfoot, marsh mallow, meristem, ginseng, and        ginger root,    -   cholesterol,    -   consistency regulators, such as sugar esters, polyol esters, or        polyol alkyl ethers,    -   fats and waxes, such as spermaceti, beeswax, montan wax, and        paraffins,    -   fatty acid alkanolamides,    -   complexing agents, such as EDTA, NTA, β-alanine diacetic acid,        and phosphonic acids (can be left out in accordance with one        embodiment of the present invention),    -   swelling and penetration agents, such as glycerol, propylene        glycol monoethyl ether, carbonates, bicarbonates, guanidines,        ureas, and primary, secondary, and tertiary phosphates,    -   opacifiers, such as latex, styrene/PVP and styrene/acrylamide        copolymers,    -   pearlizing agents, such as ethylene glycol mono- and distearate        and PEG-3 distearate,    -   pigments,    -   stabilizers for hydrogen peroxide and other oxidizing agents,    -   propellants, such as propane-butane mixtures, N₂O, dimethyl        ether, CO₂, and air, and    -   antioxidants.

With respect to other optional components and the amounts of thesecomponents to be used, reference is explicitly made to handbooks on thissubject, with which the expert is already familiar, e.g., K. Schrader,Grundlagen und Rezepturen der Kosmetika [Principles and Formulations ofCosmetics], Second Edition, Hüthig Buch Verlag, Heidelberg, 1989.

The preparations of the invention preferably contain the dyeintermediates in a suitable aqueous, alcoholic, or aqueous/alcoholicvehicle. For purposes of hair dyeing, these vehicles are, for example,creams, emulsions, gels, or surfactant-containing, foaming solutions,for example, shampoos, foaming aerosols, or other preparations that aresuitable for application to the hair. However, it is also possible tointegrate the dye precursors in a powdered or tableted formulation.

In the context of the present invention, aqueous/alcoholic solutions areunderstood to mean aqueous solutions that contain 3-70 wt. % of a C₁-C₄alcohol, especially ethanol or isopropanol. The preparations of theinvention can also contain other organic solvents, for example,methoxybutanol, benzyl alcohol, ethyl diglycol, or 1,2-propylene glycol.In this regard, all water-soluble organic solvents are preferred.

In principle, the actual oxidative dyeing of the fibers can beaccomplished with atmospheric oxygen. However, the use of a chemicaloxidizing agent is preferred, especially when a lightening effect onhuman hair is desired in addition to the dyeing. Suitable oxidizingagents are persulfates, chlorites, and especially hydrogen peroxide orits addition products with urea, melamine, and sodium borate. However,in accordance with the invention, it is also possible for the oxidationdye to be applied to the hair together with a catalyst, which activatesthe oxidation of the dye intermediates, e.g., by atmospheric oxygen.Suitable catalysts for this purpose include, for example, metal ions,iodides, quinones, or certain enzymes.

Examples of suitable metal ions are Zn²⁺, Cu²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺,Li⁺, Mg²⁺, Ca²⁺, and A³⁺. Of these metal ions, Zn²⁺, Cu²⁺ and Mn²⁺ areespecially suitable. The metal ions can be used basically in the form ofany desired, physiologically tolerated salt or in the form of a complexcompound. Preferred salts are the acetates, sulfates, halides, lactates,and tartrates. The use of these salts can both accelerate thedevelopment of the dye and systematically influence the shade of color.

Suitable enzymes are, for example, peroxidases, which can significantlyintensify the activity of small amounts of hydrogen peroxide. Inaddition, suitable enzymes in accordance with the invention are thosewhich, with the assistance of atmospheric oxygen, directly oxidize theoxidation dye intermediates, for example, the laccases, or those whichproduce small amounts of hydrogen peroxide in situ and in this waybiocatalytically activate the oxidation of the dye intermediates.Especially suitable catalysts for the oxidation of the dye intermediatesare the so-called two-electron oxidoreductases in combination with thesubstrates specific for them, e.g.:

-   -   pyranose oxidase and, e.g., D-glucose or galactose,    -   glucose oxidase and D-glucose,    -   glycerol oxidase and glycerol,    -   pyruvate oxidase and pyruvic acid or its salts,    -   alcohol oxidase and alcohol (MeOH, EtOH),    -   lactate oxidase and lactic acid and its salts,    -   tyrosinase oxidase and tyrosine,    -   uricase and uric acid or its salts,    -   choline oxidase and choline,    -   amino acid oxidase and amino acids.

It is advantageous to prepare the actual hair dye immediately beforeapplication by mixing the preparation of the oxidizing agent with thepreparation that contains the dye intermediates. The resultingready-to-use hair dye preparation preferably has a pH in the range of6-12. The application of the hair dye in a weakly alkaline environmentis especially preferred. The application temperatures can be in a rangeof 15-40° C. After the hair dye has been allowed to act for 5-45minutes, it is removed from the hair that is being dyed by rinsing itout. Subsequent washing with a shampoo is unnecessary if a vehicle witha high surfactant content, e.g., a dyeing shampoo, was used.

However, especially in the case of hair that is difficult to dye, thepreparation that contains the dye intermediates can be applied to thehair without first being mixed with the oxidation component. After ithas been allowed to act for 20-30 minutes, the oxidation component isthen applied, possibly after an intermediate rinsing of the hair. Afterthis preparation has been allowed to act for another 10-20 minutes, thehair is rinsed and, if desired, shampooed. In a first variant of thisembodiment, in which the previous application of the dye intermediatesis intended to effect better penetration of the hair, the preparation inquestion is adjusted to a pH of about 4-7. In accordance with a secondvariant, oxidation with air is strived for first, in which the appliedpreparation preferably has a pH of 7-10. In the subsequent acceleratedoxidation, the use of acid-adjusted peroxydisulfate solutions as theoxidizing agent is preferred.

EXAMPLES

The following dyeing creams are suitable especially for a dye treatmentwith the treatment devices of the invention.

The specified quantities are understood to be in wt. % unless otherwisenoted.

1. Formulation 1

Raw Material Wt. % Stenol ® 1618 3.5 Kokoslorol ® 1.5 behenyl alcohol1.0 Eumulgin ® B 1 0.3 Eumulgin ® B 2 0.3 Texapon ® NSO 10.0 Dehyton ® K5.0 Polymer JR ® 400 0.3 Gafquat ® 755 0.3 Celquat ® L 200 0.1 ascorbicacid 0.2 sodium metabisulfite 0.3 ammonium sulfate 0.4hydroxyethanediphosphonic acid (can also be 0.2 omitted from thisembodiment of the present invention) water glass solution, 40% 0.5perfume oil 0.3 p-phenylenediamine dihydrochloride 0.058p-toluylenediamine sulfate 0.17N,N-bis(2′-hydroxyethyl)-p-phenylenediamine 1.45 sulfate2-(2′-hydroxyethyl)-p-phenylenediamine sulfate 0.171,3-N,N′-bis(2′-hydroxyethyl)-N,N′-bis(4′- 0.073aminophenyl)diaminopropan-2-ol tetrahydrochloride1,10-bis(2,5-diaminophenyl)-1,4,7,10- 0.029 tetraoxadecanetetrahydrochloride 4,5-diamino-2-(2′-hydroxyethyl)pyrazole sulfate 1.203,5-diamino-2-(2-methoxyethoxy)toluene 0.253,5-diamino-4-(2-methoxyethoxy)toluene 0.073,5-bis[(2-hydroxyethyl)amino]-2-(2- 1.31 methoxyethoxy)tolueneresorcinol 0.023 2-methyl resorcinol 0.035 4-chlororesorcinol 0.0235-amino-2-methylphenol 0.011 5-(2′-hydroxyethyl)amino-2-methylphenol0.058 5-amino-4-chloro-2-methylphenol 0.283-amino-2-chloro-6-methylphenol 0.08 1-naphthol 0.0111,5-dihydroxynaphthalene 0.058 2,6-bis[(2′-hydroxyethyl)amino]toluene0.17 5,6-dihydroxyindoline hydrobromide 0.05 HC Red 1 0.034-amino-2-nitrodiphenylamine-2′-carboxylic acid 0.02 HC Red BN 0.03 HCRed B 54 0.03 Basic Red 51 0.02 ammonia, 25% To pH 10 water to 100

2. Formulation 2

Raw Material Wt. % Stenol ® 1618 3.5 Kokoslorol ® 1.5 behenyl alcohol1.0 Eumulgin ® B 1 0.3 Eumulgin ® B 2 0.3 Texapon ® NSO 10.0 Dehyton ® K5.0 Polymer JR ® 400 0.3 Gafquat ® 755 0.3 Celquat ® L 200 0.1 ascorbicacid 0.2 sodium metabisulfite 0.3 ammonium sulfate 0.4hydroxyethanediphosphonic acid (can also be 0.2 omitted from thisembodiment of the present invention) water glass solution, 40% 0.5perfume oil 0.3 p-toluylenediamine sulfate 0.182-(2′-hydroxyethyl)-p-phenylenediamine sulfate 0.18 4-aminophenol 0.024-amino-3-methylphenol 0.02 4-amino-2-aminomethylphenol dihydrochloride0.05 4-amino-2-[(diethylamino)methyl]phenol 0.03 dihydrochloridebis-(5-amino-2-hydroxyphenyl)methane 0.61 dihydrochloride2,4,5,6-tetraaminopyrimidine sulfate 0.243,5-diamino-2-(2-methoxyethoxy)toluene 0.023,5-diamino-2-[2-(2-methoxyethoxy)ethoxy]toluene 0.023,5-diamino-4-(2-methoxyethoxy)toluene 0.063,5-bis[(2-hydroxyethyl)amino]-2-(2- 1.11 methoxyethoxy)toluene3,5-bis[(2-hydroxyethyl)amino]-4-(2- 0.03 methoxyethoxy)tolueneresorcinol 0.03 resorcinol monomethyl ether 0.042-ethylamino-4-nitro-6-chlorophenol 0.03 4-amino-3-nitrophenol 0.021,4-diamino-2-nitrobenzene 0.05 Basic Yellow 87 0.01 Basic Orange 310.03 ammonia, 25% to pH 10 water to 100

3. Formulation 3

Raw Material Wt. % fatty alcohol mixture C₁₀-C₂₂ 10.0 Texapon ® K 14 S70 C 2.5 Plantaren ® 1200 UP 2.0 Akypo Soft ® 45 NV 12.0 Eutanol ® G 1.0Eumulgin ® B 1 0.5 Eumulgin ® B 2 0.5 Polymer W ® 37194 2.0 CosmediaGuar ® C 261 0.2 Mirapol ® A 15 0.5 Promois ® WK 2.0 Dow Corning ®Q2-1401 0.2 Gluadin ® WQ 1.0 ascorbic acid 0.2 EDTA disodium salt (canalso be omitted from this 0.1 embodiment of the present invention)sodium metabisulfite 0.3 ammonium sulfate 0.5 perfume oil 0.4p-phenylenediamine dihydrochloride 0.142-(2′-hydroxyethyl)-p-phenylenediamine sulfate 0.91 4-aminophenol 0.184-amino-3-methylphenol 0.05 4-amino-2-[(diethylamino)methyl]phenol 0.11dihydrochloride 2,4,5,6-tetraaminopyrimidine sulfate 1.214-hydroxy-2,5,6-triaminopyrimidine sulfate 0.173,5-diamino-2-(2-methoxyethoxy)toluene 0.0123,5-diamino-2-[2-(2-methoxyethoxy)ethoxy]toluene 0.0203,5-diamino-4-(2-methoxyethoxy)toluene 0.0403,5-bis[(2-hydroxyethyl)amino]-2-(2- 0.28 methoxyethoxy)toluene3,5-bis[(2-hydroxyethyl)amino]-4-(2- 0.014 methoxyethoxy)tolueneresorcinol 0.11 2-methyl resorcinol 0.66 4-chlororesorcinol 0.043-aminophenol 0.004 5-amino-2-methylphenol 0.0333-amino-2-chloro-6-methylphenol 0.033 3-amino-2,4-dichlorophenol 0.102-amino-3-hydroxypyridine 0.26 2,6-dihydroxy-3,4-dimethylpyridine 0.112,7-dihydroxynaphthalene 0.02 l-phenyl-3-methylpyrazol-5-one 0.02ammonia, 25% to pH 10 water to 100

4. Formulation 4

Raw Material Wt. % fatty alcohol mixture C₁₀-C₂₂ 10.0 Texapon ® K 14 S70 C 2.5 Plantaren ® 1200 UP 2.0 Akypo Soft ® 45 NV 12.0 Eutanol ® G 1.0Eumulgin ® B 1 0.5 Eumulgin ® B 2 0.5 Polymer W ® 37194 2.0 CosmediaGuar ® C 261 0.2 Mirapol ® A 15 0.5 Promois ® WK 2.0 Dow Corning ®Q2-1401 0.2 Gluadin ® WQ 1.0 ascorbic acid 0.2 EDTA disodium salt (canalso be omitted from this 0.1 embodiment of the present invention)sodium metabisulfite 0.3 ammonium sulfate 0.5 perfume oil 0.4N-[2-(4-aminophenylamino)ethyl]-N′-phenylurea 0.14 dihydrochloridep-phenylenediamine dihydrochloride 0.14 p-toluylenediamine sulfate 0.62N,N-bis(2′-hydroxyethyl)-p-phenylenediamine 0.10 sulfate4-amino-3-methylphenol 0.35 3,5-diamino-2-(2-methoxyethoxy)toluene 0.013,5-bis[(2-hydroxyethyl)amino]-2-(2- 0.03 methoxyethoxy)tolueneresorcinol 0.07 5-(2′-hydroxyethyl)amino-2-methylphenol 0.035-amino-4-chloro-2-methylphenol 0.02 3-amino-2-chloro-6-methylphenol0.58 2,4-diaminophenoxyethanol sulfate 0.0012-amino-4-(2′-hydroxyethyl)anisole sulfate 0.0011,3-bis(2′,4′-diaminophenoxy)propane 0.001 tetrahydrochloride2-amino-3-hydroxypyridine 0.15 2-methylamino-3-amino-6-methoxypyridine0.001 1-naphthol 0.02 2-methyl-1-naphthol 0.03 1,5-dihydroxynaphthalene0.05 2,6-bis[(2′-hydroxyethyl)amino]toluene 0.054-amino-2-nitro-diphenylamine-2′carboxylic acid 0.05 Basic Orange 310.05 ammonia, 25% to pH 10 water to 100

5. Formulation 5

Raw Material Wt. % fatty alcohol mixture C₁₀-C₂₂ 10.0 Texapon ® K 14 S70 C 2.5 Plantaren ® 1200 UP 2.0 Akypo Soft ® 45 NV 12.0 Eutanol ® G 1.0Eumulgin ® B 1 0.5 Eumulgin ® B 2 0.5 Polymer W ® 37194 2.0 CosmediaGuar ® C 261 0.2 Mirapol ® A 15 0.5 Promois ® WK 2.0 Dow Corning ®Q2-1401 0.2 Gluadin ® WQ 1.0 ascorbic acid 0.2 EDTA disodium salt (canalso be omitted from this 0.1 embodiment of the present invention)sodium metabisulfite 0.3 ammonium sulfate 0.5 perfume oil 0.4p-toluylenediamine sulfate 0.91N,N-bis(2′-hydroxyethyl)-p-phenylenediamine 0.05 sulfate2-(2′-hydroxyethyl)-p-phenylenediamine sulfate 0.251,3-N,N′-bis(2′-hydroxyethyl)-N,N′-bis(4′- 0.01aminophenyl)diaminopropan-2-ol tetrahydrochloride1,10-bis(2,5-diaminophenyl)-1,4,7,10- 0.01 tetraoxadecanetetrahydrochloride 4-amino-2-[(diethylamino)methyl]phenol 0.10dihydrochloride 3,5-diamino-2-(2-methoxyethoxy)toluene 0.103,5-bis[(2-hydroxyethyl)amino]-2-(2- 0.14 methoxyethoxy)tolueneresorcinol 0.35 3-aminophenol 0.10 1,3-bis(2′,4′-diaminophenoxy)propane0.005 tetrahydrochloride 2-methylamino-3-amino-6-methoxypyridine 0.0203,5-diamino-2,6-dimethoxypyridine 0.005 4-hydroxyindole 0.016-hydroxyindole 0.01 5,6-dihydroxyindoline hydrobromide 0.10 ammonia,25% to pH 10 water to 100

6. Formulation 6

Raw Material Wt. % Stenol ® 1618 4.5 Behenyl alcohol 1.0 Kokoslorol ®2.5 Texapon ® NSO 2.0 Dehyton ® K 1.0 potassium oleate 2.0 potassiumisostearate 2.0 potassium myristate 1.0 Westvaco Diacid ® H 240 K salt2.0 Merquat ® 550 0.2 Luviquat ® FC 370 0.1 Merquat ® 280 0.1 Gafquat ®HS 100 0.1 ascorbic acid 0.4 hydroxyethanediphosphonic acid (can also be0.2 omitted from this embodiment of the present invention) perfume oil0.4 4-aminophenol 0.02 4-amino-2-aminomethylphenol dihydrochloride 0.044-amino-2-[(diethylamino)methyl]phenol 0.04 dihydrochloridebis-(5-amino-2-hydroxyphenyl)methane 1.00 dihydrochloride2,4,5,6-tetraaminopyrimidine sulfate 0.273,5-bis[(2-hydroxyethyl)amino]-2-(2- 1.17 methoxyethoxy)toluene1,2,3,4-tetrahydro-6-nitroquinoxaline 0.04 HC Yellow 5 0.02 HC Red BN0.03 2-ethylamino-4-nitro-6-chlorophenol 0.01 4-amino-3-nitrophenol 0.01HC Red B 54 0.03 Acid Red 52 0.05 Acid Red 33 0.05 ammonia, 25% to pH 10water to 100

7. Formulation 7

Raw Material wt. % Stenol ® 1618 6.0 behenyl alcohol 1.5 Kokoslorol ®6.0 Eumulgin ® B 1 3.0 Eumulgin ® B 2 3.0 Eumulgin ® HRE 40 1.0Polydiol ® 400 5.0 Aminoxyd ® WS 35 1.0 EDTA disodium salt (can also beomitted from this 0.1 embodiment of the present invention) Natrosol ®250 HHR 1.0 ammonium sulfate 0.4 ascorbic acid 0.1Hydroxyethanediphosphonic acid 0.2 perfume oil 0.3 p-phenylenediaminedihydrochloride 0.06 p-toluylenediamine sulfate 0.20N,N-bis(2′-hydroxyethyl)-p-phenylenediamine 0.18 sulfate2-(2′-hydroxyethyl)-p-phenylenediamine sulfate 0.291,3-N,N′-bis(2′-hydroxyethyl)-N,N′-bis(4′- 0.03aminophenyl)diaminopropan-2-ol tetrahydrochloride1,10-bis(2,5-diaminophenyl)-1,4,7,10- 0.06 tetraoxadecanetetrahydrochloride bis-(5-amino-2-hydroxyphenyl)methane 0.20dihydrochloride 3,5-bis[(2-hydroxyethyl)amino]-2-(2- 0.70methoxyethoxy)toluene 3,5-bis[(2-hydroxyethyl)amino]-4-(2- 0.08methoxyethoxy)toluene HC Red 1 0.02 HC Red BN 0.05 HC Red B 54 0.05Basic Yellow 87 0.02 Basic Orange 31 0.10 Basic Red 51 0.15 ammonia, 25%to pH 10 water to 100

8. Formulation 8

Raw Material Wt. % Edenor ® PK 1805 7.0 Texapon ® NSO 4.0 coco fattyalcohol 7.5 Dehydol ® LS 2 8.0 Isopropanol 14.5 sodium metabisulfite 0.1ascorbic acid 0.1 hydroxyethanediphosphonic acid (can also be 0.1omitted from this embodiment of the present invention) L-arginine 1.0Monoethanolamine 8.0 Salcare ® SC 96 0.1 perfume oil 0.3p-phenylenediamine dihydrochloride 0.07 p-toluylenediamine sulfate 0.09N,N-bis(2′-hydroxyethyl)-p-phenylenediamine 0.05 sulfate2-(2′-hydroxyethyl)-p-phenylenediamine sulfate 0.052,4,5,6-tetraaminopyrimidine sulfate 0.504-hydroxy-2,5,6-triaminopyrimidine sulfate 0.043,5-bis[(2-hydroxyethyl)amino]-2-(2- 0.96 methoxyethoxy)toluene1,2,3,4-tetrahydro-6-nitroquinoxaline 0.10 HC Yellow 5 0.02 HC Red 10.01 HC Red BN 0.01 2-ethylamino-4-nitro-6-chlorophenol 0.034-amino-3-nitrophenol 0.04 HC Red B 54 0.02 1,4-diamino-2-nitrobenzene0.05 Acid Red 52 0.03 Acid Red 33 0.03 ammonia, 25% to pH 10 water to100

The formulations 1 to 8 are preferably allowed to dye completely withthe following oxidizing agent preparation: dipicolinic acid 0.1 wt. %sodium pyrophosphate 0.03 wt. % Turpinal ® SL (can also be omitted from1.50 wt. % this embodiment of the present invention) Texapon ® N28 2.00wt. % Acrysol ® 22 0.60 wt. % hydrogen peroxide, 50% 2.00 wt. % sodiumhydroxide, 45% 0.80 wt. % water to 100 wt. %

9. Example 9

Raw Material Amount aqueous ammonium Carbopol solution (1%) 15.0Lanette ® E 0.70 lauryl ether sulfate (27% aqueous solution) 4.40 PEG400 0.60 potassium oleate (12.5% aqueous solution) 3.00 titanium dioxide0.50 cetylstearyl alcohol 50/50 12.00 Eumulgin ® B2 3.00 Eutanol ® G2.00 Cutina ® AGS 2.00 Cutina ® GMS-SE 2.00 XF42-B1989 1.50 potassiumhydroxide (50% in water) 0.48 tetrasodium EDTA (can also be omitted fromthis 0.40 embodiment of the present invention) sodium sulfite 0.10ascorbic acid 0.05 Merquat Plus ® 3330 2.00 perfume 0.50 ammonia (25%aqueous solution) 6.00 Aerosil ® 200 0.25 p-toluylenediamine sulfate0.460 resorcinol 0.200 m-aminophenol 0.026 2,6-diaminopyridine 0.0102,4-diaminophenoxyethanol dihydrochloride 0.012 water to 100

10. Example 10 to 12

Example 10 11 12 Raw Material Amount Amount Amount aqueous ammoniumCarbopol 15.00 15.00 15.00 solution (1%) Lanette ® E 0.70 0.70 0.70lauryl ether sulfate (27% 4.40 4.40 4.40 aqueous solution) PEG 400 0.604.60 4.60 potassium oleate (12.5% aqueous 3.00 3.00 3.00 solution)titanium dioxide 0.50 0.50 0.50 cetylstearyl alcohol 50/50 12.00 12.0012.00 Eumulgin ® B2 3.00 3.00 3.00 Eutanol ® G 2.00 2.00 2.00 Cutina ®AGS 2.00 2.00 2.00 Cutina ® GMS-SE 2.00 2.00 2.00 XF42-B1989 1.50 1.501.50 Potassium hydroxide (50% in 1.00 — — water) tetrasodium EDTA (canalso be 0.40 0.40 0.40 omitted from this embodiment of the presentinvention) sodium sulfite 0.15 — — ascorbic acid 0.10 0.05 0.05 MerquatPlus ® 3330 2.00 2.00 2.00 perfume 0.50 0.50 0.60 AMP-100 — 3.94 7.80ammonia (25% aqueous solution) 6.00 6.00 7.50 Aerosil ® 200 0.25 0.250.25 p-aminophenol 0.200 — — p-toluylenediamine sulfate 0.960 — —resorcinol 0.450 — — m-aminophenol 0.030 — — 5-amino-2-methylphenol0.060 — — 1,2-diamino-4-nitrobenzene — 0.350 0.400 water to 100 to 100to 100

11. Example 13

Raw Material Amount aqueous ammonium Carbopol solution (1%) 15.0Lanette ® E 0.70 lauryl ether sulfate (27% aqueous solution) 4.40 PEG400 0.60 potassium oleate (12.5% aqueous solution) 3.00 titanium dioxide0.50 cetylstearyl alcohol 50/50 12.00 Eumulgin ® B2 3.00 Eutanol ® G2.00 Cutina ® AGS 2.00 Cutina ® GMS-SE 2.00 XF42-B1989 1.50 potassiumhydroxide (50% in water) 0.28 tetrasodium EDTA (can also be omitted fromthis 0.40 embodiment of the present invention) sodium sulfite 0.10ascorbic acid 0.05 Merquat Plus ® 3330 2.00 perfume 0.50 AMP-100 5.00ammonia (25% aqueous solution) 6.50 Aerosil ® 200 0.25 p-aminophenol0.015 p-toluylenediamine sulfate 0.260 5-amino-2-methylphenol 0.2502,4-diaminophenoxyethanol dihydrochloride 0.020 water to 100

Examples 14 to 16

Example 14 15 16 Raw Material Amount Amount Amount aqueous ammoniumCarbopol 15.00 15.00 15.00 solution (1%) Lanette ® E 0.70 0.70 0.70lauryl ether sulfate (27% 4.40 4.40 4.40 aqueous solution) PEG 400 0.600.60 0.60 potassium oleate (12.5% aqueous 3.00 3.00 3.00 solution)titanium dioxide 0.50 0.50 0.50 cetylstearyl alcohol 50/50 12.00 12.0012.00 Eumulgin ® B2 3.00 3.00 3.00 Eutanol ® G 2.00 2.00 2.00 Cutina ®AGS 2.00 2.00 2.00 Cutina ® GMS-SE 2.00 2.00 2.00 XF42-B1989 1.50 1.501.50 potassium hydroxide (50% in 1.00 0.60 0.28 water) tetrasodium EDTA(can also be 0.40 0.40 0.40 omitted from this embodiment of the presentinvention) sodium sulfite 0.10 0.10 0.08 ascorbic acid 0.10 0.10 0.05Merquat Plus ® 3330 2.00 2.00 2.00 perfume 0.50 0.50 0.50 ammonia (25%aqueous solution) 6.00 6.00 6.00 Aerosil ® 200 0.25 0.25 0.25p-aminophenol 0.070 0.035 0.024 p-phenylenediamine 0.780 0.510 0.220dihydrochloride resorcinol 0.540 0.330 0.140 m-aminophenol 0.085 0.0290.011 water to 100 to 100 to 100

The formulations 9 to 16 are preferably allowed to dye completely withthe following oxidizing Raw Material Amount stearyl trimethylammoniumchloride 0.75 Eumulgin ® B2 1.20 Lanette ® O 4.00 propylene glycol 0.50liquid paraffin 0.50 Turpinal ® SL (can also be omitted from this 0.20embodiment of the present invention) sodium benzoate 0.10 phenacetin0.10 Na₂HPO₄ 0.04 hydrogen peroxide (35% in water) 17.00 water to 100 PH3.0

12. Examples 17 to 19

Dyeing Dyeing Dyeing Cream Cream Cream Raw Material 17 18 191,2-propylene glycol 6.8 6.8 6.8 tetrasodium EDTA (can also be 0.3 0.30.3 omitted from this embodiment of the present invention) ascorbic acid0.1 0.1 0.1 sodium sulfite 0.3 0.3 0.3 perfume 0.5 0.5 0.5 ammonia, 25%6.0 6.0 6.0 myristyl alcohol 0.9 0.9 0.9 cetearyl alcohol 7.1 7.1 7.1hydrogenated castor oil 0.7 0.7 0.7 glyceryl stearate 1.2 1.2 1.2laureth-23 0.3 0.3 0.3 ceteareth-30 0.9 0.9 0.9 cetrimonium chloride 2.12.1 2.1 isopropyl myristate 3.0 3.0 3.0 p-toluylenediamine sulfate 1.84— 5.2 m-aminophenol 0.24 0.36 0.36 resorcinol 0.66 — 1.76 2-amino-4-(2-0.04 — 0.18 hydroxyethyl) aminoanisole sulfate 1-(2-hydroxyethyl)-4,5- —1.35 — diaminopyrazole 4-amino-3-methylphenol — 0.14 —5-amino-2-methylphenol — 0.41 — KOH, aqueous to pH to pH to pH 10.3 10.610.0 water, demineralized to 100 to 100 to 100 shade of the dyeing lightfiery black brown red

13. Example 20

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid EFA 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 2.41 resorcinol 0.86 3-aminophenol 0.261-methoxy-2-amino-4-(2-hydroxyethylamino) 0.11 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 9.0ascorbic acid 0.06 Mirapol ® A15 0.19 perfume 0.43 water to 100.00

14. Example 21

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid EFA 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 2.12 resorcinol 0.63 3-aminophenol 0.201-methoxy-2-amino-4-(2-hydroxyethylamino) 0.05 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 10.0ascorbic acid 0.06 cetyltrimethylammonium bromide 0.50 perfume 0.43water to 100.00

15. Example 22

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid EFA 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 0.84 resorcinol 0.21 3-aminophenol 0.054-chlororesorcinol 0.15 1,2-propylene glycol USP 1.05 methoxybutanol1.43 ammonia, 25% in water to pH 10.5 ascorbic acid 0.06 Rewoquat ® W 75PG 0.30 perfume 0.43 water to 100.00

16. Example 23

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid EFA 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.22p-toluylenediamine 1.33 resorcinol 0.48 3-aminophenol 0.101-methoxy-2-amino-4-(2-hydroxyethylamino) 0.02 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 9.5ascorbic acid 0.06 Polymer JR ® 400 1.00 perfume 0.43 water to 100.00

17. Example 24

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid SV 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 2.41 resorcinol 0.86 3-aminophenol 0.261-methoxy-2-amino-4-(2-hydroxyethylamino) 0.11 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 9.0ascorbic acid 0.06 Gafquat ® 755N 0.50 perfume 0.43 water to 100.00

18. Example 25

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid SV 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 2.12 resorcinol 0.63 3-aminophenol 0.201-methoxy-2-amino-4-(2-hydroxyethylamino) 0.05 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 8.9ascorbic acid 0.06 Crotein ® C 0.30 perfume 0.43 water to 100.00

19. Example 26

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid SV 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) Silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 0.84 resorcinol 0.21 3-aminophenol 0.054-chlororesorcinol 0.16 1,2-propylene glycol USP 1.05 methoxybutanol1.43 ammonia, 25% in water to pH 9.0 ascorbic acid 0.06 Gluadin ® WK0.70 perfume 0.43 water to 100.00

20. Example 27

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid PTC 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 2.41 resorcinol 0.86 3-aminophenol 0.261-methoxy-2-amino-4-(2-hydroxyethylamino) 0.11 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 9.1ascorbic acid 0.06 Merquat ® 280 0.20 perfume 0.43 water to 100.00

21. Example 28

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid PTC 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) 0.46 silicic acid, highly disperse, pyrogenic 0.11p-toluylenediamine 2.12 resorcinol 0.63 3-aminophenol 0.201-methoxy-2-amino-4-(2-hydroxyethylamino) 0.05 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 9.1ascorbic acid 0.06 Jaguar ® C-17 0.30 perfume 0.43 water to 100.00

22. Example 29

Ammonium Carbopol solution, 1% in water 17.25 Ammonium Rohagit solution,6% in water 5.25 Oleth-7 5.70 potassium olein soap, 12.5% in water 12.75potassium castor oil soap, 12.5% in water 3.45 Plantaren ® 2000 0.53titanium dioxide anatase, type AS 05 0.48 Cetiol ® V 3.45 cetyl alcohol16.80 glycerol monostearate NSE 2.85 Phospholipid PTC 0.85 tetrasodiumEDTA (can also be omitted from 0.46 this embodiment of the presentinvention) silicic acid, highly disperse, pyrogenic 0.22p-toluylenediamine 1.33 resorcinol 0.48 3-aminophenol 0.101-methoxy-2-amino-4-(2-hydroxyethylamino) 0.02 benzene 1,2-propyleneglycol USP 1.05 methoxybutanol 1.43 ammonia, 25% in water to pH 9.0ascorbic acid 0.06 Mirapol ® A15 0.19 perfume 0.43 water to 100.00

23. List of Commercial Products Used

The commercial products used in the examples are defined as follows:Acid Red 33 C.I. 17200 Acid Red 52 C.I. 45100 Acrysol ® 22 Acrylicpolymer (ca. 29.5-30.5% solids in water; INCI name:Acrylates/Steareth-20 Methacrylate Copolymer) Aerosil ® 200 Pyrogenicsilicic acid (INCI name: Silica) (Degussa) Akypo Soft 45 NV ® Laurylalcoho1-4.5-EO-acetic acid sodium salt (at least 21% active substancecontent; INCI name: Sodium Laureth-6 Carboxylate) (Chem-Y) Aminoxyd ® WS35 N,N-dimethyl-N(C₈₋₁₈ cocoacylamidopropyl)amine-N-oxide (ca. 35%active substance in water; INCI name: • Cocamidopropylamine Oxide)(Goldschmidt) Ammonium Carbopol Solution of an ammonium salt of amethacrylic acid/methacrylate copolymer (INCI name: AmmoniumPolyacrylate) (Röhm GmbH) Ammonium Rohagit Solution of an ammonium saltof an acrylic acid polymer (INCI name: Ammonium Acrylate Copolymer)(Goodrich) Basic Orange 31 Azo dye (CIBA) Basic Red 51 Azo dye (CIBA)Basic Yellow 87 Methine dye (CIBA) Celquat ® L 200 Quaternized cellulosederivative (INCI name: Polyquaternium-4) (National Starch) Cetiol ® VDecyl oleate (INCI name: Decyl Oleate) (Henkel) Cosmedia Guar ® Guarhydroxypropyltrimethylammonium C 261 chloride (at least 93% solids; INCIname: Guar Hydroxypropyltrimonium Chloride) (Cognis CorporationCosmedia) Crotein ® C Gelatin hydrolysate (ca. 93% active substance;INCI name: Hydrolyzed Collagen) (Croda) Cutina ® ACS Ethylene glycoldistearate (INCI name: Glycol Distearate) (Cognis) Cutina ® GMS-SEGlycerol monodistearate/potassium stearate mixture of plant origin (INCIname: Glyceryl Stearates SE) (Cognis) Dehydol ® LS 2 C₁₂₋₁₄ fattyalcohol with ca. 2 EO units (INCI name: Laureth-2) (Cognis Pulcra)Dehyton ® K N,N-Dimethyl-N—(C₈₋₁₈ cocamidopropyl)ammonium acetobetaine(ca. 30% active substance; INCI name: Aqua (Water), CocamidopropylBetaine) (Cognis) Dow CorningDimethylcyclosiloxane/dimethylpolysiloxanol Q2-1401 ® mixture (ca. 13%solids; INCI name: Cyclomethicone, Dimethiconol) (Dow Corning) Edenor ®PK 1805 Oleic acid (INCI name: Oleic Acid) (Cognis) Eumulgin ® B1Cetylstearyl alcohol with ca. 12 EO units (INCI name: Ceteareth-12)(Cognis) Eumulgin ® B2 Cetylstearyl alcohol with ca. 20 EO units (INCIname: Ceteareth-20) (Cognis) Eumulgin ® HRE 40 Hydrogenated castor oilwith ca. 40 EO units (INCI name: PEG-40 Hydrogenated Castor Oil)(Cognis) Eutanol ® G 2-Octyldodecyl alcohol (INCI name: Octyldodecanol)(Cognis) Gafquat ® 755 Dimethylaminoethyl methacrylate/vinylpyrrolidonecopolymer, quaternized with diethyl sulfate (ca. 19% solids in water;INCI name: Polyquaternium-11) (ISP) Gafquat ® HS 100Vinylpyrrolidone/methacrylamidopropyltrimethyl- ammonium chloridecopolymer (19-21% active substance in water; INCI name: Polyquaternium-28) (ISP) Gluadin ® WK Wheat protein hydrolysate-fatty acid condensate(ca. 30% active substance; INCI name: Sodium Cocoyl Hydrolyzed WheatProtein) (Henkel) Gluadin ® WQ Wheat protein hydrolysate (ca. 31-35%solids; INCI name: Aqua (Water), Laurdimonium Hydroxypropyl HydrolyzedWheat Protein, Ethylparaben, Methylparaben) (Cognis) Glycerol mono- NSE(INCI name: Glyceryl Stearate) stearate (Oleofina) HC Red 12-Amino-2-nitrodiphenylamine HC Red B 544-[(2-hydroxyethyl)amino]-3-nitrophenol (INCI name: 3-nitro-p-hydroxyethylaminophenol) HC Red BN4-[(3-hydroxypropyl)amino]-3-nitrophenol HC Yellow 5N¹-(2-hydroxyethyl)-4-nitro-1,2- phenylenediamine Hydrenol ® D C₁₆₋₁₈fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis) Jaguar ® C-17 Guarhydroxypropyltrimethylammonium chloride (INCI name: GuarHydroxypropyltrimonium Chloride) (Rhodia Inc.) Kokosloral ® C₁₂₋₁₈ fattyalcohol (INCI name: Coconut Alcohol) (Cognis) Lanette ® E Cetylstearylalcohol sulfate sodium salt (INCI name: Sodium Cetearyl Sulfate)(Cognis) Lanette ® O C₁₆₋₁₈ fatty alcohol (INCI name: Cetearyl Alcohol)(Cognis) Lorol ® tech. C₁₂₋₁₈ fatty alcohol (INCI name: Coconut Alcohol)(Cognis) Luviquat ® Vinylimidazoliummethyl FC 370chloride/vinylpyrrolidone copolymer (30:70) (38-42% solids in water;INCI name: Polyquaternium-16) (BASF) Merquat ® 280Dimethyldiallylammonium chloride/acrylic acid copolymer (ca. 35% activesubstance in water; INCI name: Polyquaternium-22) (Ondeo-Nalco)Merquat ® 550 Dimethyldiallylammonium chloride/acrylamide copolymer (ca.8.1- 9.1% active substance in water; INCI name: Polyquaternium-7)(Ondeo-Nalco) Merquat Plus ® Dimethyldiallylammonium chloride/acrylic3330 acid/acrylamide terpolymer (ca. 9.5% active substance content; INCIname: Polyquaternium-39) (Ondeo-Nalco) Mirapol ® A 15Poly[N-(3-(dimethylammonium)propyl]-N′-[3-ethyleneoxyethylenedimethylammonium)propyl]- urea dichloride (ca. 64%solids in water; INCI name: Polyquaternium-2) (Rhodia) Natrosol ® 250Hydroxyethyl cellulose (INCI name: HHR hydroxyethylcellulose) (Hercules)Oleth-7 Oleyl alcohol with 7 EO units (Henkel) Phospholipid EFA (ca. 30%active substance; INCI name: Linoleamidopropyl PG-Dimonium ChloridePhosphate) (Mona) Phospholipid PTC (ca. 47% active substance; INCI name:Cocamidopropyl PG-Dimonium Chloride Phosphate) (Mona) Phospholipid SV(ca. 41.5% active substance; INCI name: Stearamidopropyl PG-DimoniumChloride Phosphate (and) Cetyl Alcohol) (Mona) Plantaren ® C₁₂-C₁₆ fattyalcohol-1,4-glucoside 1200 UP unpreserved, boron-free (ca. 50-53% activesubstance) (Cognis Corporation (Emery)) Plantaren ® 2000C₈₋₁₈-alkyl-1,4-polyglucoside (ca. 51% active substance; INCI name:Decyl Glucoside) (Henkel) Polydiol ® 400 Polyethylene glycol (INCI name:PEG-8) (Cognis) Polymer JR ® 400 Quaternized hydroxyethyl cellulose(INCI name: Polyquaternium-10) (Amerchol) Polymer ® W ca. 20 wt. %active substance content in 37194 water; INCI name:Acryamidopropyltrimonium Chloride/Acrylates Copolymer (Stockhausen)Promois ® WK Keratin hydrolysate (INCI name: Aqua (Water), HydrolyzedKeratin, Methylparaben, Propylparaben) (Seiwa (Interorgana)) Rewoquat ®W 1-Methyl-2-nortallow alkyl-3-tallow fatty 75 PGacidamidoethylimidazolinium methosulfate (ca. 75% active substance inpropylene glycol; INCI name: Quaternium 27) (Witco Surfactants GmbH)Salcare ® SC 96 ca. 50% active substance content; INCI name:Polyquaternium-37, Propylene Glycol Dicaprylate/Dicaprate, PPG-1Trideceth-6 (CIBA) Stenol ® 1618 C₁₆₋₁₈ fatty alcohol (INCI name:Cetearyl Alcohol) (Cognis) Texapon ® EVR Lauryl ether sulfate sodiumsalt with special additives (ca. 34-37% active substance content; INCIname: Sodium Lauryl Sulfate, Sodium Laureth Sulfate, Lauramide MIPA,Cocamide MEA, Glycol Stearate, Laureth-10) (Cognis) Texapon ® K 14Laurylmyristyl ether sulfate sodium salt S 70 C (ca. 68-73% activesubstance content; INCI name: Sodium Myreth Sulfate) (Cognis) Texapon ®N28 Lauryl ether sulfate sodium salt (at least 26.5% active substancecontent; INCI name: Sodium Laureth Sulfate) (Cognis) Texapon ® NSOLauryl ether sulfate sodium salt (ca. 27.5% active substance content;INCI name: Sodium Laureth Sulfate) (Cognis) Turpinal ® SL1-Hydroxyethane-1,1-diphosphonic acid (ca. 58-61% active substancecontent; INCI name: Etidronic Acid, Aqua. (Water)) (Solutia) WestvacoDiacid ® 4-Hexyl-5(6)-carboxy-2-cyclohexene-1- H 240 octanoic acidpotassium salt (ca. 41% active substance in water) (Westvaco Chemicals)XF42-B1989 amino-functional silicone (INCI name: Amodimethicone)(GE-Toshiba Silicones)

1. A device for treating keratin fibers, which comprises a vibrationgenerator for generating vibrations; and a vibration transmitter, whichis connected with the vibration generator, for transmitting vibrationsto the keratin fibers; wherein the vibration transmitter has a firstsection and a second section; wherein the first section and the secondsection can be brought into a treatment position, in which the keratinfibers are secured between the first section and the second section; andwherein, during the treatment, the vibrations are transmitted to thekeratin fibers by at least one of the two sections in the clampedposition.
 2. The device in accordance with claim 1, wherein the firstand second sections of the vibration transmitter have surfaces that arearranged essentially parallel to each other in the clamped position. 3.The device in accordance with claim 1 wherein the vibration transmitterhas the form of a clip or clamp.
 4. The device in accordance with claim1 wherein the first and second sections of the vibration transmitterhave dimensions such that a tuft of keratin fibers wrapped in foil isenclosed by the first and second sections essentially along a length ofthe keratin fibers.
 5. The device in accordance with claim 1 wherein thefirst or the second section of the vibration transmitter consistsessentially of an aluminum material.
 6. The device in accordance withclaim 1 wherein the first and second sections of the vibrationtransmitter consist of wire-like elements.
 7. The device in accordancewith claim 6 wherein the vibration transmitter is stationary relative tothe keratin fibers arranged in the vibration transmitter during thetreatment.
 8. The device in accordance with claim 1 wherein the keratinfibers are human hair.
 9. The device in accordance with claim 8 whereina large number of vibration transmitters is provided, each of which isconnected with the vibration generator; wherein a stand is provided, onwhich the vibration transmitters can be placed in a resting position insuch a way that they are arranged near the head of a person whose hairis to be treated; wherein the vibration transmitters can each beattached to a tuft of hair of a person during a treatment; and whereinthe vibration generator is installed on the stand.
 10. The device inaccordance with claim 1 wherein the vibration generator is designed togenerate at least one vibration with a frequency in the range of about 3kHz to about 200 kHz.
 11. The device in accordance with claim 1 whereinthe vibration generator is designed to generate at least one vibrationin the ultrasonic range.
 12. The device in accordance with claim 11wherein the vibration generator is designed to generate at least onevibration with a frequency in the range of about 3 kHz to about 20 kHz.13. The device in accordance with claim 12 wherein the vibrationgenerator is designed to generate at least one vibration with afrequency on the order of 5 kHz.
 14. The device in accordance with claim1 wherein the keratin fibers are secured in such a way between the firstand second sections of the vibration transmitter that the vibrationtransmitter does not slip from the keratin fibers during the treatmentdue to its own weight.
 15. A method for treating keratin fibers, whichcomprises the following steps: attaching a vibration transmitter, whichis connected with a vibration generator and is designed for transmittingvibrations to keratin fibers, to the keratin fibers in such a way thatthe keratin fibers are arranged between a first and second section ofthe vibration transmitter, wherein the keratin fibers are securedbetween the first and second sections; and transmission of thevibrations from at least one of the two sections to the keratin fibersby the vibration transmitter.
 16. The method in accordance with claim 15wherein the keratin fibers are hair; wherein a large number of vibrationtransmitters is arranged on the hair, and each vibration transmitter isconnected with the vibration generator; and wherein the large number ofvibration transmitters is mounted in a resting position on a stand insuch a way that the vibration transmitters are arranged near the head ofa person whose hair is to be treated and can be removed from the standand attached to individual tufts of hair.
 17. The method in accordancewith claim 15 wherein an agent for changing the color of the keratinfibers, which contains no chelates, is applied to the keratin fibers.18. The method in accordance with claim 16 wherein the agent helpstransmit vibrations from the vibration transmitter to the keratinfibers.
 19. The method in accordance with claim 15 wherein thevibrations have a frequency in the range of about 3 kHz to about 200kHz.
 20. The method in accordance with claim 18 wherein the vibrationshave a frequency in the ultrasonic range.
 21. The method in accordancewith claim 19 wherein the vibrations have a frequency in the range ofabout 3 kHz to about 20 kHz.
 22. The method in accordance with claim 20wherein the vibrations have a frequency on the order of 5 kHz.
 23. Adevice for treating hair, which comprises: a hood that is designed to atleast partially enclose regions of the head of a person whose hair is tobe treated; a vapor generator for producing vapor, wherein the vaporgenerator is connected with the hood; wherein the hood has holes toapply the vapor to regions of the head; a vibration generator forgenerating vibrations; wherein the vibration generator acts togetherwith the vapor generator in such a way that the vibrations aretransmitted to the vapor or through the vapor; wherein the vapor, to orthrough which the vibrations have been at least partially transmitted,is applied through the hood to hair in the corresponding regions of thehead.
 24. The device in accordance with claim 22 wherein the vibrationgenerator is designed to generate at least one vibration with afrequency in the range of about 3 kHz to about 200 kHz.
 25. The devicein accordance with claim 22 wherein the vibration generator is designedto generate at least one vibration in the ultrasonic range.
 26. Thedevice in accordance with claim 22 wherein the vibration generator isdesigned to generate at least one vibration with a frequency in therange of about 3 kHz to about 20 kHz.
 27. The device in accordance withclaim 25 wherein the vibration generator is designed to generate atleast one vibration with a frequency on the order of 35 kHz.
 28. Amethod for treating keratin fibers, which comprises the following step:transmission of the vibrations to the keratin fibers by means of vapor.29. The method in accordance with claim 27 wherein a first agent forchanging the color of the keratin fibers, which contains no chelates, isapplied to the keratin fibers.
 30. The method in accordance with claim27 further comprising a second agent, which supports the transmission ofvibrations from the vapor to the keratin fibers, is applied to thekeratin fibers.
 31. The method in accordance with claim 27 wherein thevibrations have a frequency in the range of about 3 kHz to about 200kHz.
 32. The method in accordance with claim 27 wherein the vibrationshave a frequency in the ultrasonic range.
 33. The method in accordancewith claim 31 wherein the vibrations have a frequency in the range ofabout 3 kHz to about 20 kHz.
 34. The method in accordance with claim 27wherein the vibrations have a frequency on the order of 35 kHz.
 35. Adevice for treating hair, which comprises vibration transmission means,which surround large portions of the hair region of a person's head;wherein the vibration transmission means transmit vibrations to thehair.
 36. The device in accordance with claim 34 wherein the vibrationtransmission means are formed as partially elastic fingers so as to atleast partially surround the region of the head that is covered withhair.
 37. The device in accordance with claim 34 wherein the vibrationshave a frequency in the range of about 3 kHz to about 200 kHz.
 38. Thedevice in accordance with claim 34 wherein the vibrations have afrequency in the ultrasonic range.
 39. The device in accordance withclaim 37 wherein the vibrations have a frequency in the range of about 3kHz to about 20 kHz.
 40. The device in accordance with claim 38 whereinthe vibrations have a frequency on the order of 5 kHz.
 41. A method fortreating keratin fibers, which comprises the step of transmittingvibrations to the keratin fibers.
 42. The method in accordance withclaim 40 wherein a first agent for changing the color of the keratinfibers, which contains no chelates, is applied to the keratin fibers.43. The method in accordance with claim 40 further comprising a secondagent, which supports the transmission of vibrations to the keratinfibers, is applied to the keratin fibers.
 44. The method in accordancewith claim 40 wherein the vibrations have a frequency in the range ofabout 3 kHz to about 200 kHz.
 45. The method in accordance with claim 43wherein the vibrations have a frequency in the ultrasonic range.
 46. Themethod in accordance with claim 40 wherein the vibrations have afrequency in the range of about 3 kHz to about 20 kHz.
 47. The method inaccordance with claim 45 wherein the vibrations have a frequency on theorder of 5 kHz.
 48. An agent for changing the color of keratin fibers,wherein the agent contains no chelating agents.